Hetero cyclic metallocene compounds and use thereof in catalyst system for producing olefin polymers

ABSTRACT

A metallocene compound of general formula (I): LGZMXp, wherein L is a divalent group, Z is a moiety of formula (II), wherein R 3  and R 4  are selected from hydrogen and hydrocarbon groups; A and B are selected from S, O or CR 5 , wherein R 5  is selected from hydrogen and hydrocarbon groups, either A or B being different from CR 5 ; G is a moiety of formula (III), wherein R 6 , R 7 , R 8  and R 9  are selected from hydrogen and hydrocarbon groups, M is an atom of a transition metal, X is selected from a halogen atom, a R 10 , OR 10 , OSO 2 CF 3 , OCOR 10 , SR 10 , NR 10   2  or PR 10   2  group, wherein the substituents R 10  is hydrogen and a hydrocarbon group; p is an integer from 0 to 3.

This application is the U.S. national phase of International Application PCT/EP00/13191, filed Dec. 22, 2000.

The present invention relates to a new class of metallocene compounds, to catalysts containing them and to a process carried out in the presence of said catalysts for the preparation of polymers of alpha-olefins, particularly propylene polymers, having a low degree of crystallinity. The present invention also relates to the ligands for those metallocenes and to a convenient process for their preparation.

Products of propylene homopolymerization can have varying degrees of crystallinity. The type and amount of crystallinity is largely dependent on the microstructure of the polypropylene. Polypropylene having predominantly isotactic or syndiotactic structure is partially crystalline, while polypropylene having predominantly atactic structure is amorphous. Propylene polymers are also known which have a reduced degree of crystallinity and show elastomeric properties. U.S. Pat. No. 4,335,225, for instance, discloses a fractionable, elastic polypropylene, having an isotactic content of 55% or less, which contain a diethyl ether-soluble fraction with an isotactic crystalline content of about 0.5–5% by weight. This polypropylene is prepared with a catalyst based on a tetraalkyl zirconium supported on a metal oxide. However, the elastomeric polypropylenes of this type, due to the fact that the catalyst systems which are used for their preparation have different catalytic sites, are endowed with a wide distribution of molecular weights which has a negative impact on their properties.

Metallocene catalysts have recently been used in the polymerization reaction of olefins. Operating in the presence of these catalysts, polymers characterized by a narrow molecular weight distribution and having structural characteristics of interest have been obtained. By polymerizing propylene in the presence of metallocene catalysts, amorphous or highly crystalline polypropylenes can be obtained depending on the metallocene used.

Certain metallocene catalysts are also known that can produce partially crystalline elastomeric polypropylene. International application WO 95/25757, for instance, describes unbridged metallocene catalysts that can produce isotactic-atactic stereoblock polypropylenes having elastomeric thermoplastic properties. Despite the homogeneity in molecular weight distribution, the tacticity distribution of these polymers is not homogeneous. Moreover, the activity is low. U. Dietrich et al. in “J. Am. Chem. Soc. 1999, 121, 4348–4355” describe metallocene catalysts that are able to produce thermoplastic elastic polypropylenes.

More recently, heterocyclic metallocene compounds have been used in the polymerization of alpha-olefins. International application WO 98/22486 discloses a class of metallocenes containing a cyclopentadienyl radical directly coordinating the central metal atom, to which are fused one or more rings containing at least one heteroatom. These metallocenes, in combination with a suitable cocatalyst, are used in the polymerization of olefins such as propylene. The working examples relate to the preparation of highly stereoregular polypropylene.

It would be desirable to provide a novel class of metallocenes which, when used in catalysts for the polymerization of olefins, in particular propylene, are capable of yielding polymers endowed with high molecular weights, narrow molecular weight distribution and a reduced degree of crystallinity. It would be most desirable to provide metallocene catalysts that can produce those polymers with high activity, such that the amount of catalyst remaining in the formed polymer is minimized.

A novel class of metallocene compounds has now been unexpectedly found, which achieves the above and other results.

According to a first aspect the present invention provides a metallocene compound of general formula (I): LGZMX_(p)  (I) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² and (CR¹R²)₂, R¹ and R², which may be the same as or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-arylalkyl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, R¹ and R² can also form a ring having 3 to 8 atoms which can bear substituents;

Z is a moiety of formula (II):

wherein R³ and R⁴, which may be the same as or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-arylalkyl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, preferably at least one of R³ and R⁴ being different from hydrogen;

A and B are selected from sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, i.e. either A or B being different from CR⁵, and wherein the rings containing A and B have a double bond in the allowed position being two aromatic rings;

G is a moiety of formula (III):

wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are selected from the group consisting of hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, R⁶ and R⁷ and/or R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, which can bear substituents;

with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical R⁸ is not hydrogen;

M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements (new IUPAC version), X, same or different, is selected from a hydrogen atom, a halogen atom, a group R¹⁰; OR¹⁰, OSO₂CF₃, OCOR¹⁰, SR¹⁰, NR¹⁰ ₂ or PR¹⁰ ₂, wherein the substituents R¹⁰ are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-arylalkyl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements;

p is an integer from 0 to 3, preferably from 1 to 3, being equal to the formal oxidation state of the metal M minus 2;

isopropylidene(3-trimethylsilylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, dimethylsilanediyl(3-trimethylsilylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, isopropylidene(3-ethylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, dimethylsilanediyl(3-ethylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, isopropylidene(3-n-butylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, dimethylsilanediyl(3-n-butylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, isopropylidene(3-methylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, dimethylsilanediyl(3-methylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride, isopropylidene(3-i-propylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride and dimethylsilanediyl(3-i-propylcyclopentadienyl)(7-cyclopentadithiophene)zirconium dichloride being excluded.

The transition metal M is preferably selected from titanium, zirconium and hafnium preferably having a formal oxidation state of +4. The X substituents are preferably chlorine atoms, benzyl or methyl groups. Preferably the bridging group L is a CMe₂ or SiMe₂ group. Preferably A or B is a sulfur atom and the other is a CH group, more preferably A is sulfur and B is a CH group. Preferably R³ and R⁴ are the same and are selected from a C₁–C₂₀-alkyl group, which can contain a silicon atom. Most preferably R³ and R⁴ are a methyl, an ethyl, a phenyl or a trimethylsilyl radical.

Non-limiting examples of metallocene compounds according to the present invention are:

methylene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(3-ethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(3-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(2,4-diisopropyl-cyclopentadienyl)-7-(2,5-dimethylyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(2,3,5-triethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(2,3,5-triisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(3-cyclohexyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(indenyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(3-ter-butyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(2,3-dimethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(3-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

methylene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-ethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2-methyl-4-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2,4-diisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2,3,5-triethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(2,3,5-triisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-cyclohexyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene-1-(2,3-dimethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene-1tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-methyl-cyclopentadienyl)-4-(2,6-dimethylcyclopentadienyl-[2,1-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-isopropyl-cyclopentadienyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

methylene(3-methyl-cyclopentadienyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)hafnium dichloride and dimethyl;

isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-ethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcylopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2,4-diisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-[b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2-methyl-4-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2-methyl-4-phenyl-cyclopentadienyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2-methyl-4-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2,3,5-triethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(2,3,5-triisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-cyclohexyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-isopropyl-cyclopentadienyl)-4-(2,6-dimethylcyclopentadienyl-[2,1-b:3,4-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene-1-(3-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene-1-(2,3-dimethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene-1-(3-tert-butyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b :4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-methyl-cyclopentadienyl)-4-(2,6-dimethylcyclopentadienyl-[2,1-b:3,4-b′]dithiophene)hafnium dichloride and dimethyl;

dimethylsilandiyl(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-ethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,4-diisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,3,5-triethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,3,5-triisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-cyclohexyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-trimethylsilyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(2,3-dimethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-ethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-isopropyl-indenyl)-4-(2,6-dimethylcyclopentadienyl-[2,1-b:3,4-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-isopropyl-indenyl)-7-(2,5-ditrimethylsilylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)hafnium dichloride and dimethyl;

dimethylsilandiyl-1-(3-tertbutyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dithiophene)zirconium dichloride and dimethyl;

isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(3-ethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(3-phenyl-cyclopentadienyl)-7-(2,5-dimethylyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(2,4-diisopropyl-cyclopentadienyl)-7-(2,5ethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(2,3,5-triethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(2,3,5-triisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(3-cyclohexyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-1-(indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-1-(3-methyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-1-(3-ethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-2-(3-tert-butyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)hafnium dichloride and dimethyl;

dimethylsilandiyl(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-ethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-phenyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,4-diisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2; -b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,3,5trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,3,5-triethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(2,3,5-triisopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-cyclohexyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(indenyl)-7-(2,5-methylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol) zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-methyl-indenyl)-7-(2,5-b]ethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(2,3-dimethyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

dimethylsilandiyl-1-(tetrahydroindenyl)-7-(2,5-dimethylcyclopentadienyl-[1,2-b:4,3-b′]dioxazol)zirconium dichloride and dimethyl;

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)hafnium dichloride; and dimethyl

A particularly interesting class of bridged metallocenes of formula (I) according to the present invention is that wherein G is a moiety of formula (IIIa):

wherein R⁶ and R⁹ equal to or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, preferably R⁶ is hydrogen and R⁹ is different from hydrogen;

R⁷ is selected from a C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl or a QR¹¹R¹²R¹³ group, wherein Q is selected from C, Si, Ge;

R¹¹, R¹² and R¹³, which may be the same as or different from each other, are hydrogen, C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-arylalkyl radicals, optionally containing a heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, with the proviso that when Q is a carbon atom, at least one of R¹¹, R¹² and R¹³ is a hydrogen atom.

Particularly preferred metallocenes of the above mentioned class are those wherein R⁷ is selected from a phenyl group, a CHR¹¹R¹² group and a SiR¹¹R¹²R¹³ group, R¹¹, R¹² and R¹³ being hydrogen or C₁–C₂₀-alkyl groups.

Most preferred are those metallocene wherein QR¹¹R¹²R¹³ is an isopropyl or a trimethylsilyl group.

Non-limiting examples of this class of metallocenes are:

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

dimethylsilandiyl(3-trimethylsilyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(2-methyl-4-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(3-isopropyl-cyclopentadienyl)-7-(2,5-ditrimethylsilyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(3-isopropyl-cyclopentadienyl)-4-(2,6-dimethyl-cyclopentadienyl-[2,1-b:3,4-b′]-dithiophene)zirconium dichloride;

isopropylidene(2-methyl-4-phenyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(3-phenyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(2-methyl-4-phenyl-cyclopentadienyl)-7-(2,5-ditrimethylsilyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

isopropylidene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-ditrimethylsilyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

dimethylsilandiyl(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride; and

isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)hafnium dichloride.

Another advantageous class of bridged metallocenes of formula (I) is that wherein G is a moiety of formula (IV):

wherein

T¹ is a sulfur atom or a CR¹⁶ group;

T² is a carbon atom or a nitrogen atom;

z is 1 or 0;

the ring containing T¹ and T² has double bonds in the allowed position;

with the proviso that if z is 1, T¹ is a CR¹⁶ group and T² is a carbon atom and the ring formed is a benzene ring; and if z is 0, T² bonds directly the cyclopentadienyl ring, the 5 membered ring formed has double bonds in any of the allowed position having an aromatic character and T¹ and T² are not at the same time, a sulfur atom and a nitrogen atom.

R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, the which may be the same as or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms which can bear substituents.

An advantageous subclass of compounds belonging to the above class is that wherein G is a moiety of formula (IVa):

wherein R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, which may be the same as or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms, and any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms which can bear substituents and the benzene ring can be perhydrated.

Non-limiting examples of metallocenes belonging to this class are:

dimethylsilandiyl-1-(indenyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride;

dimethylsilandiyl-1-(2-methyl-indenyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b′]-dithiophene)zirconium dichloride.

A preferred structure of compounds of formula (IVa) has the formula (IVb):

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and any of two adjacent R¹⁴, R¹⁶, R¹⁷ and R¹⁸ can form a ring comprising 4 to 8 atoms which can bear substituents; R¹⁴ is selected from the group consisting of C₁–C₂₀-alkyl or C₆–C₂₀-aryl group such as a methyl ethyl, or phenyl group;

Preferably when G is a moiety of formula (IVb) L is a group SiR¹R^(2,) wherein R¹ and R² have the meaning described above, more preferably L is SiMe₂.

A further preferred structure of compounds of formula (IVa) has the formula (IVc)

wherein R¹⁴, R¹⁶, R¹⁷, and R¹⁸ are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, optionally any of two adjacent R¹⁴, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms which can bear substituents;

R¹⁹ is selected from the group consisting of C₁–C₂₀alkyl or C₆–C₂₀aryl group such as a methyl, ethyl, or phenyl group or forms with R¹⁸ a benzene ring that can bears substituents.

Preferably R¹⁴ is selected from the group consisting of C₁–C₂₀alkyl or C₆–C₂₀-aryl group such as a methyl, ethyl, or phenyl group; preferably R¹⁶ is selected from the group consisting of C₁–C₂₀-alkyl or C₆–C₂₀-aryl group such as a methyl, ethyl, or phenyl group

Preferably when G is a moiety of formula (IVc) L is a group SiR¹R², wherein R¹ and R² have the meaning described above, more preferably L is SiMe₂.

Another advantageous subclass of compounds wherein G is a moiety of formula (IV) is that wherein G is a moiety of formula (IVd)

wherein:

T¹ is a sulfur atom or a CR¹⁶ group;

T² is a carbon atom or a nitrogen atom; the 5 membered ring formed by T¹ and T² has double bonds in any of the allowed position, having an aromatic character;

with the proviso that if T¹ is a sulphur atom T² is not a nitrogen atom;

R¹⁴, R¹⁷ and R¹⁸ which may be the same as or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and R¹⁷and R¹⁸ can form a ring comprising 4 to 8 atoms which can bear substituents.

Particularly preferred are those compounds wherein T² is a carbon atom; T¹ is sulphur and R¹⁴, R¹⁷ and R¹⁸ equal to or different from each other are C₁–C₂₀alkyl, C₆–C₂₀-aryl; preferably R¹⁴, R¹⁷ and R¹⁸ are methyl or phenyl groups.

Preferably when G is a moiety of formula (IVd) L is a group SiR¹R², wherein R¹ and R² have the meaning described above, more preferably L is SiMe₂

According to another aspect of the present invention there is provided a class of ligands of formula (V): LG′Z′  (V) wherein L is defined as described above;

Z′ is a moiety of formula (VI):

and its double bond isomers;

wherein A, B, R³ and R⁴ are defined as described above and the double bonds are in any of the allowed position;

G′ is a moiety of formula (VII):

and its double bond isomers;

wherein R⁶, R⁷, R⁸ and R⁹ have the meaning as defined above.

The ligand of formula (V) can be prepared according to the procedure known in the art, in particular when R⁴ and R³ are both hydrogen the ligand of formula (V) can be prepared as described in WO 98/22486.

According to a further aspect of the present invention a process is provided for the preparation of a ligand of formula (V) comprising the following steps:

-   a) contacting a compound of the formula (VIII) with a base selected     from the group consisting of metallic sodium and potassium, sodium     and potassium hydroxide and an organolithium compound, wherein the     molar ratio between the compound of the formula (VIII) and said base     is at least 1:1

-    wherein A, B, R³ and R⁴ are described above; -   b) contacting the obtained anionic compounds of formula (VIII) with     a compound of formula (IX):

-    wherein L, R⁶, R⁷, R⁸ and R⁹ are defined as above and Y is a     halogen radical selected from the group consisting of chloride,     bromide and iodide, preferably chlorine and bromine.

When L is CR¹R² the ligand of formula (V) can be obtained by an alternative process comprising the following steps:

-   a) contacting a compound of the formula (VIII) with a base selected     from the group consisting of metallic sodium and potassium, sodium     and potassium hydroxide and an organolithium compound, wherein the     molar ratio between the compound of the formula (VIII) and said base     is at least 1:1;

-   b) contacting the obtained anionic moiety of the formula (VI) with a     compound of formula (X):

-    wherein R¹, R², R⁶, R⁷, R⁸ and R⁸ have the meaning as defined     above; and then treating the obtained product with a protonating     agent.

The base used in step a) of both processes is preferably methyllithium or n-butyllithium. Preferably the protonating agent used in the above process is a quaternary ammonium salt and most preferably the protonating agent is ammonium chloride.

Non limiting examples of the compound of formula (X) is selected from 6,6-dimethylfulvene and 3-isopropyl-6,6-dimethylfulvene.

Non-limiting examples of compounds of formula (IX) are (3-methyl-cyclopentadienyl)dimethylchlorosilane, (3-isopropyl-cyclopentadienyl)dimethyl chlorosilane, 1-(3-methyl-cyclopentadienyl)-1,1-dimethyl-2,2-dimethyl-2-chloro-ethane and 1-(3-isopropyl-cyclopentadienyl)-1,1-dimethyl-2,2-dimethyl-2-chloro-ethane.

The compound of formula (VIII) in the case where B is a CR⁵ can be obtained by a process comprising the following steps:

-   -   i) treating a compound of formula (XI):

-   -    wherein A is sulfur or oxygen, with a compound of formula         (XII):

-   -    wherein A is sulfur or oxygen,     -   ii) contacting the thus obtained product with a reducing agent         in a molar ratio between said reducing agent and the product         obtained under i) of at least 1;     -   iii) contacting the product obtained under ii) with a compound         selected from an organolithium compound, sodium and potassium in         a molar ratio between said compound and the product obtained in         step ii) of equal to or greater than 2;     -   iv) treating the thus obtained product with an agent selected         from the group consisting of copper chloride, copper iodide and         Mg/Pd., in order to obtain a compound of general formula (XIII):

When B is sulfur or oxygen and A is a CR⁵ group the compound of formula (VIII) can be obtained according to the process comprising the following steps:

-   -   i) contacting a compound of formula (XIV):

-   -    wherein B is sulfur or oxygen,         -   with a compound of formula (XV):

-   -   -    wherein B is sulfur or oxygen,             -   and subsequently treating with a neutralization agent;

    -   ii) treating the thus obtained product with a reducing agent in         a molar ratio between said reducing agent and the compound         obtained under i) of at least 1;

    -   iii) contacting the thus obtained product with a mixture of an         organolithium compound and tetramethylethylenediamine (TMEDA) in         a molar ratio between said mixture and the product obtained         under ii) of at least 2,

    -   iv) contacting the thus obtained product with an agent selected         from the group consisting of copper chloride, copper iodide and         Mg/Pd., in order to obtain a compound of formula (XVI):

An alternative process for preparing the compound of formula (VIII) when A is S or O comprises the following steps:

-   -   i) contacting an equimolar mixture of compounds of         formulae (XVII) and (XVIII):

-   -    wherein A are sulfur or oxygen,         -   with a Lewis acid or a mixture of a Lewis acid and a             protonic acid;     -   ii) treating the thus obtained product with CH₂O in a molar         ratio between said mixture and CH₂O within a range between 10:1         and 1:10;     -   iii) contacting the thus obtained product with a compound         selected from an organolithium compound, sodium and potassium;     -   iv) contacting the thus obtained product with an agent selected         from the group consisting of copper chloride, iodine and Mg/Pd.,         in order to obtain a compound of general formula (XIII).

The Lewis acid used in the above process is preferably selected from zinc dichloride, cadmium dichloride, mercury dichloride, tin tetrachloride, trifluoroborane, zirconium tetrachloride and titanium tetrachloride. Most preferably, the Lewis acid is zinc dichloride.

The agent used in the above processes of the invention is preferably copper chloride.

Preferably the reducing agent is a mixture of AlCl₃/LiAlH₄.

The organic lithium compound used above is preferably butyllithium.

Another alternative process for preparing the compound of formula (VIII) when A is S or O comprises the following steps:

-   -   i) contacting a compound of formula (XIX):

-   -    with a base selected from an organolithium compound, sodium or         potassium; treating the obtained product with a formic ester,         wherein the molar ratio between said ester and the compound of         formula (XIX) is at least 1:2, and subsequently treating the         obtained product with a reducing agent in order to obtain a         compound of formula (XX):

-   -   ii) contacting the compound of formula (XX) with a base selected         from an organolithium compound, sodium or potassium and         subsequently treating the dimetallated compound with an         alkylating agent to obtain the compound of formula (XXI);

-   -    or alternatively treating the dimetallated compound with an         ester of boric acid and a protonating agent in order to obtain         the compound of formula (XXII):

-   -    and subsequently contacting with a mixture of an alkylating         agent in the presence of an transition metal complex compound         for obtaining the compound of formula (XXI);     -   iii) contacting the alkylated compound obtained by step b) with         a coupling agent; in order to obtain the compound of formula         (XIII).

Preferably the alkylating agent is selected from dimethylsulphate Me₂SO₄), trimethylchlorosilane (Me₃SiCl) and a mixture of compounds of formulae R³Y′ and R⁴Y′, wherein R³ and R⁴ are defined as above and Y′ is selected from chloride, bromide and iodide, preferably Y′ is a chlorine. Preferably the transition metal complex compound is PdCl₂ (dppf).

In the above-described processes the reducing agent is preferably a mixture of AlCl₃/LiAlH₄ or a mixture of triethylsilane (Et₃SiH) and CF₃COOH. The preferred the base is butyllithium.

Preferably the organic acid ester is an ester of formic acid. Preferably the coupling agent is selected from the group consisting of copper chloride, copper iodide and Mg/Pd.

All the reactions are carried out in aprotic solvents. Non limiting examples of aprotic solvents suitable for the above reported processes are tetrahydrofurane, dimethoxyethane, diethylether, toluene, dichloromethane, pentane, hexane and benzene.

During the whole process, the temperature is generally kept between −100° C. and 80° C., preferably between −20° C. and 40° C.

Compounds of formula (V) can be suitable used as intermediates for the preparation of metallocenes of formula (I).

Therefore, a still further aspect of the present invention is a process for the preparation of a metallocene compound of formula (I), obtainable by contacting the ligand of general formula (V), with a compound capable of forming the corresponding dianionic compound and thereafter with a compound of general formula MX_(p+2), wherein M, X and p are defined as above.

The compound able to form said corresponding dianionic compound is selected from the group consisting of hydroxides of alkali- and alkaline-earth metals, metallic sodium and potassium, and organometallic lithium salts.

Preferably, the compound able to form said corresponding dianionic compound is butylithium.

Non-limiting examples of compounds of formula MX_(p+2) are titanium-, zirconium- and hafnium tetrachloride.

More specifically, the ligand of formula (V) is dissolved in a polar aprotic solvent and to the obtained solution is added a solution of an organolithium compound in an apolar solvent. The thus obtained anionic compound is optionally separated, dissolved or suspended in a polar aprotic solvent and thereafter added to a suspension of the compound MX_(p+2) in a polar aprotic solvent. At the end of the reaction, the solid product obtained is separated from the reaction mixture by techniques commonly used in the state of the art such as filtration or recrystallization.

Non limiting examples of polar aprotic solvents suitable for the above reported processes are tetrahydrofurane, dimethoxyethane, diethylether and dichloromethane. Non limiting examples of apolar solvents suitable for the above process are pentane, hexane, benzene and toluene. Throughout the process, the temperature is generally kept between −100° C. and 80° C., preferably between −20° C. and 40° C.

In the case in which at least one substituent X in the metallocene compound of the formula (I) is different from halogen an alternative process for preparing it consists in preparing the dihalogen derivative, i.e. the complex wherein both X substituents are halogen, and then substituting the halogen atoms with the appropriate X groups by the methods generally applied. For example, if the desired substituents X are alkyl groups, the metallocenes can be made by reaction with alkylmagnesium halides (Grignard reagents) or with alkyllithium compounds. General methods for substituting X with substituents other than halogen such as sulfur, phosphorus, oxygen, etc. are described in Chem. Rev. 1994, 94, 1661–1717, and the cited references therein.

According to a still further aspect of the present invention a catalyst for the polymerization of alpha-olefins is provided, obtainable by contacting:

-   (A) a metallocene compound of formula (I)     LGZMX_(p)  (I) -    wherein L, Z, M, X, and p has been defined above and G is a moiety     of formula (III):

-    wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different     from each other, are selected from the group consisting of hydrogen,     a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl,     C₇–C₂₀-alkylaryl, C₇–C₂₀arylalkyl radical, optionally containing     heteroatoms belonging to groups 13–17 of the Periodic Table of the     Elements, R⁶ and R⁷ and/or R⁸ and R⁹ can form a ring comprising from     3 to 8 atoms, which can bear substituents; with the proviso that R⁷     is different from R⁸ and when R⁷ is a tertbutyl radical R⁸ is not     hydrogen; and -   (B) an alumoxane and/or a compound capable of forming an alkyl     metallocene cation. Preferably in the metallocene compound of     formula (I) G is a moiety of formula (IIIa) or (IV), more preferably     G is a moiety selected from the compound of formula (IIIa), (IVb),     (IVc) or (IVd).

The alumoxane used as component (B) can be obtained by reacting water with an organo-aluminium compound of formula H_(j)AlR²³ _(3−j)or H_(j)Al₂R²³ _(6−j), where R²³ substituents, same or different, are hydrogen atoms, C₁–C₂₀-allyl, C₃–C₂₀-cyclalkyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl or C₇–C₂₀-arylalkyl, optionally containing silicon or germanium atoms with the proviso that at least one R²³ is different from halogen, and J ranges from 0 to 1, being also a non-integer number. In this reaction the molar ratio of Al/water is preferably comprised between 1:1 and 100:1.

The molar ratio between aluminium and the metal of the metallocene is comprised between about 10:1 and about 20000:1, and more preferably between about 100:1 and about 5000:1.

The alumoxanes used in the catalyst according to the invention are considered to be linear, branched or cyclic compounds containing at least one group of the type:

wherein the substituents R²³, same or different, are described above.

In particular, alumoxanes of the formula:

can be used in the case of linear compounds, wherein n is 0 or an integer from 1 to 40 and the substituents R are defined as above, or alumoxanes of the formula:

can be used in the case of cyclic compounds, wherein u is an integer from 2 to 40 and the R²³ substituents are defined as above.

Examples of alumoxanes suitable for use according to the present invention are methylalumoxane (MAO), tetra-(isobutyl)alumoxane (TIBAO), tetra-(2,4,4trimethyl-pentyl)alumoxane (TIOAO), tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and tetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO).

Particularly interesting cocatalysts are those described in WO 99/21899 and in PCT/EP00/09111 in which the alkyl and aryl groups have specific branched patterns.

Non-limiting examples of aluminium compounds according to said PCT applications are:

tris(2,3,3-trimethyl-butyl)aluminum, tris(2,3-dimethyl-hexyl)aluminium, tris(2,34dimethyl-butyl)aluminium, tris(2,3-dimethyl-pentyl)aluminium, tris(2,3-dimethyl-heptyl)aluminium, tris(2-methyl-3-ethyl-pentyl)aluminium, tris(2-methyl-3-ethyl-hexyl)aluminium, tris(2-methyl-3-ethyl-heptyl)aluminium, tris(2-methyl-3-propyl-hexyl)aluminium, tris(2-ethyl-3-methyl-butyl)aluminium, tris(2-ethyl-3-methyl-pentyl)aluminium, tris(2,3-diethyl-pentyl)aluminium, tris(2-propyl-3-methyl-butyl)aluminium, tris(2-isopropyl-3-methyl-butyl)aluminium, tris(2-isobutyl-3-methyl-pentyl)aluminium, tris(2,3,3-trimethyl-pentyl)aluminium, tris(2,3,3-trimethyl-hexyl)aluminium, tris(2-ethyl-3,3-dimethyl-butyl)aluminium, tris(2-ethyl-3,3-dimethyl-pentyl)aluminium, tris(2-isopropyl-3,3-dimethyl-butyl)aluminium, tris(2-trimethylsilyl-propyl)aluminium, tris(2-methyl-3-phenyl-butyl)aluminium, tris(2-ethyl-3-phenyl-butyl)aluminium, tris(2,3-dimethyl-3-phenyl-butyl)aluminium, tris(2-phenyl-propyl)aluminum, tris[2-(4-fluoro-phenyl)-propyl]aluminium, tris[2-(4-chloro-phenyl)-propyl]aluminium, tris[2-(3-isopropyl-phenyl)-propyl]aluminium, tris(2-phenyl-butyl)aluminium, tris(3-methyl-2-phenyl-butyl)aluminium, tis(2-phenyl-pentyl)aluminium, tris[2-(pentafluorophenyl)-propyl]aluminium, tris[2,2-diphenyl-ethyl]aluminium and tris[2-phenyl-2-methyl-propyl]aluminium, as well as the corresponding compounds wherein one of the hydrocarbyl groups is replaced with a hydrogen atom, and those wherein one or two of the hydrocarbyl groups are replaced with an isobutyl group.

Amongst the above aluminium compounds, trimethylaluminum (TMA), triisobutylaluminum (TBAL), tris(2,4,trimethyl-pentyl)aluminium (TIOA), tris(2,3-dimethylbutyl)aluminium (TDMBA) and tris(2,3,3-trimethylbutyl)aluminium (TTMBA) are preferred.

Non-limiting examples of compounds able to form an alkylmetallocene cation are compounds of formula D⁺E⁻, wherein D⁺ is a Brønsted acid, able to donate a proton and to react irreversibly with a substituent X of the metallocene of formula (I) and E⁻ is a compatible anion, which is able to stabilize the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be able to be removed by an olefinic monomer. Preferably, the anion E⁻ consists of one or more boron atoms. More preferably, the anion E⁻ is an anion of the formula BAr₄ ⁽⁻⁾, wherein the substituents Ar which can be identical or different are aryl radicals such as phenyl, pentafluorophenyl or bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl borate is particularly preferred. Moreover, compounds of the formula BAr₃ can conveniently be used. Compounds of this type are described, for example, in the published International patent application WO 92100333. Further, compounds of the formula RM′-O-M′R, R being an alkyl or aryl group, and M′ is selected from an element of the Group 13 of the Periodic Table of the Elements (new IUPAC version). Compounds of this type are described, for example, in the International patent application WO 99/40129.

The catalysts of the present invention can also be supported on an inert carrier. This is achieved by depositing the metallocene compound (A) or the product of the reaction thereof with the component (B), or the component (B) and then the metallocene compound (A) on supports such as, for example, silica, alumina, magnesium halides, styrene/divinylbenzene copolymers, polyethylene or polypropylene. The supportation process is carried out in an inert solvent such as hydrocarbon for example toluene, hexane, pentane or propane and at a temperature ranging from 0° C. to 100° C., preferably the process is carried out at room temperature.

A suitable class of supports which can be used is that constituted by porous organic supports functionalized with groups having active hydrogen atoms. Particularly suitable are those in which the organic support is a partially crosslinked styrene polymer. Supports of this type are described in European application EP-633272.

Another class of inert supports particularly suitable for use according to the invention is that of the olefin, particularly propylene, porous prepolymers described in International application WO 95/26369.

A further suitable class of inert supports for use according to the invention is that of porous magnesium halides such as those described in International application WO 95/32995.

The solid compound thus obtained, in combination with the further addition of the alkylaluminium compound either as such or prereacted with water if necessary, can be usefully employed in the gas-phase polymerization.

According to a still further aspect of the present invention a process is provided for the preparation of polymers of alpha-olefins comprising contacting one or more alpha-olefins under polymerization conditions with a catalyst comprising the product obtainable by contacting:

-   (A) a metallocene compound of formula (I)     LGZMX_(p)  (I) -    wherein L, Z, M, X, and p has been defined above and G is a moiety     of formula (III):

-    wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different     from each other, are selected from the group consisting of hydrogen,     a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl,     C₇–C₂₀-alkylaryl, C₇–C₂₀-arylalkyl radical, optionally containing     heteroatoms belonging to groups 13–17 of the Periodic Table of the     Elements, R⁶ and R⁷ and/or R⁸ and R⁹ can form a ring comprising from     3 to 8 atoms, which can bear substituents; with the proviso that R⁷     is different from R⁸ and when R⁷ is a tert-butyl radical R⁸ is not     hydrogen; and -   (B) an alumoxane and/or a compound capable of forming an alkyl     metallocene cation.

Preferably in the metallocene compound of formula (I) G is a moiety of formula (IIIa) or (IV), more preferably G is a moiety selected from the compound of formula (IIIa), (IVB), (IVc) or (IVd).

The process for the polymerization of olefins according to the invention can be carried out in the liquid phase in the presence or absence of an inert hydrocarbon solvent, or in the gas phase. The hydrocarbon solvent can either be aromatic such as toluene, or aliphatic such as propane, hexane, heptane, isobutane or cyclohexane.

The polymerization temperature is generally comprised between −100° C. and +100° C. and, particularly between 10° C. and +90° C. The polymerization pressure is generally comprised between 0,5 and 100 bar.

The lower the polymerization temperature, the higher are the resulting molecular weights of the polymers obtained.

The polymerization yields depend on the purity of the metallocene compound of the catalyst. The metallocene compounds obtained by the process of the invention can therefore be used as such or can be subjected to purification treatments.

The components of the catalyst can be brought into contact with each other before the polymerization. The pre-contact concentrations are generally between 0.1 and 10⁻⁸ mol/l for the metallocene component (A), while they are generally between 2 and 10⁻⁸ mol/l for the component (B). The pre-contact is generally effected in the presence of a hydrocarbon solvent and, if appropriate, of small quantities of monomer. It the pre-contact it is also possible to use a non-polymerizable olefin such as isobutene, 2-butene and the like.

Further, the molecular weights of the polymer obtained, in particular of propylene homo or polymers, 1-butene polymers or ethylene homo or copolymers, are distributed over relatively limited ranges. The molecular weight distribution can be represented by the ratio Mw/Mn which, for the present polymers, is generally lower than 4, preferably lower than 3.5 and, more preferably, lower than 3.

The molecular weight distribution can be varied by using mixtures of different metallocene compounds or by carrying out the polymerization in several stages which differ as to the polymerization temperature and/or the concentrations of the molecular weight regulators.

One of the preferred alpha-olefins to be used in the polymerization process of the present invention is propylene. When propylene is polymerized and G is a moiety selected from the compound of formula (IIIa) and (IVb) a propylene polymer having a melting enthalpy <70 J/g; and triads (mm) satisfying the relation: 30<mm<85 can generally be obtained. When G is a moiety selected from the compound of formula (IVc), (IVd) the polymer obtained generally have a catalyst activity and/or intrinsic viscosity higher than those obtained with similar catalyst used in the prior art. For example in J. Am. Chem. Soc. 1998, 120, 10786–10787 isopropylidene{(3-tertbutyl-cyclopentadienyl)-7-(2,5-ditrimethylsilyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride was used for polymerizing propylene, with a catalyst activity of only 13 Kg/mmol cath. The polymers obtained generally have the triads (mm) satisfying the relation: 70<mm<95 preferably 85<mm<95 and an intrinsic viscosity (I.V. measured in tetrahydronaphtalene (THN) solution) higher than 0.7 preferably 0.8, more preferably higher than 1, even more preferably higher than 2.

More interesting propylene polymers obtainable with the process described above are propylene polymer having the following characteristics:

-   -   triads (mm) satisfying the relation 30<mm<85 preferably 55<mm<85         and more preferably 65<mm<85     -   melting enthalpy (ΔH)<70 J/g, preferably comprised between 5 J/g         and 70 J/g more preferably comprised between 20 J/g and 70 J/g.

The molecular weights of the above said propylene polymers can be quite high. Thus, the intrinsic viscosity can reach values of greater than 0.7 dl/g, preferably greater than 1 dl/g, more preferably greater than 2.

The propylene polymers described above are endowed with good balance between optical properties, being quite transparent and elastomeric properties. Thus the polypropylene of the present invention has the following properties:

-   -   Haze (ASTM 2457) from 15% to 30%, preferably from 20% to 30%;     -   Gloss (60° C.) (ASTM 2457) from 60% to 95%, preferably from 70%         to 85%;     -   Tensile modulus (ASTM D4065) from 1000 Mpa to 200 Mpa,         preferably from 700 Mpa to 400 Mpa;     -   Elongation at break (ASTM D4065) from 300% to 900%, preferably         from 500% to 700%;     -   Strength at break (ASTM D638) from 10% to 40%, preferably from         10% to 30%.

The microstructures of polypropylene obtained by the process of the present invention, cover a range of commercial copolymers such as elastomeric, flexible, and random-like polypropylene, but with the difference that the melting point of the polypropylene of the present invention is always higher than the cited copolymer. Thus polypropylene of the present invention can easily replace these more expensive copolymers.

The polymerization reaction of propylene according to the invention can be carried out in the presence of ethylene or of a C₄–C₁₀ alpha-olefin comonomer. Thus a further aspect of the present invention is a propylene copolymer containing from 0.1 to 30% by moles, preferably from 0.1 to 20% by moles, more preferably from 0.1 to 10% by moles, even more preferably from 0.1 to 5% by moles of units deriving from an olefin of formula CH₂═CHR′, R′ being hydrogen, a C₂–C₂₀-alkyl or a C₆–C₁₂-aryl group, said propylene copolymer having the following characteristics:

-   -   melting enthalpy<70 J/g, preferably<50 J/g;     -   triads (mm) of the polypropylene homosequences satisfy the         relation: 30<mm<85, preferably55 <mm<85.

Non-limiting examples of alpha-olefins which can be used as comonomers in the copolymers according to the present invention are ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, styrene, 1,5-hexadiene and 1,7-octadiene. A preferred comonomer is ethylene.

The process according to the present invention is also suitable for obtaining ethylene homo and copolymers wherein the olefin comonomers can be alpha-olefins, cyclolefins or polyenes. Ethylene homopolymers having a remarkably high molecular weight are obtainable. In fact, with the process of the present invention it is possible to obtain ethylene polymers having intrinsic viscosity (I.V.) values as high as 5.0 dl/g and even higher.

In the copolymers obtainable with the process of the invention, the molar content of ethylene derived units is generally higher than 40%, and preferably it is comprised between 50% and 99%, and most preferably it is comprised between 80% and 98%.

The molar content of alpha-olefin derived units is preferably comprised between 0% and 60% and, more preferably, between 1% and 50%, and most preferably between 2% and 20%.

Non-limiting examples of alpha-olefins which can be used as alpha-olefins in the process of the invention are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and allylcyclohexane.

Non-limiting examples of cycloolefins that can be used as comonomers in the process of the present invention are cyclopentene, cyclohexene and norbornene.

The copolymers according to the invention can also contain units derived from polyenes. The content of polyene derived units, if any, is preferably comprised between 0% and 30 mol % and, more preferably between 0% and 20 mol %.

The polyenes that can be used as comonomers in the copolymers according to the present invention are included in the following classes:

-   -   non-conjugated diolefins able to cyclopolymerize such as, for         example, 1,5-hexadiene, 1-6-heptadiene, 2-methyl-1,5-hexadiene;     -   dienes capable of giving unsaturated monomeric units, in         particular conjugated dienes such as, for example, butadiene and         isoprene, and linear non-conjugated dienes, such as, for         example, trans 1,4-hexadiene, cis 1,4-hexadiene,         6-methyl-1,5-heptadiene, 3,7-dimethyl-1,6-octadiene,         11-methyl-1,10-dodecadiene, and cyclic non-conjugated dienes         such as 5-ethylidene-2-norbornene

The metallocenes of the present invention can also be used for the polymerization in gas phase of ethylene with alpha-olefins such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and allylcyclohexane.

In the case of ethylene/propylene copolymers, the product of the reactivity ratios r₁.r₂, wherein r₁ is the reactivity ratio of propylene and r₂ that of ethylene, is calculated according to the following formula: r ₁ r ₂=1+f(χ+1)−(f+1).(χ+1)^(1/2) wherein

f=ratio between moles of ethylene units and moles of propylene units in the copolymer, and χ=(PPP+PPE)/EPE.

The molecular weight of the polymers can be varied by varying the type or the concentration of the catalyst components or using molecular weight regulators such as, for example, hydrogen.

The tacticity of the polymer chain, i.e. the distribution of the relative configuration of the tertiary carbons, is determined by NMR analysis as described by Resconi et al Chem. Rev. 2000, 100, 1253–1345 and reference cited therein.

The polymers of the invention are transformable into shaped articles by conventional material processing, such as molding, extrusion, injection etc. The polymers of the present invention can be used for the preparation of synthetic leather, roofing blends, geomembranes, transparent objects, foam beds, as additive for bitumen or as polymer support for pigments and/or colors in masterbatches.

EXAMPLES General Procedures

All operations were performed under nitrogen by using conventional Schlenk-line techniques. Solvents were purified by degassing with N₂ and passing over activated (8 hours, N₂ purge, 300° C.) Al₂O₃, and stored under nitrogen. n-BuLi (Aldrich) was used as received.

The proton and carbon spectra of ligands and metallocenes were obtained using a Bruker DPX 200 spectrometer operating in the Fourier transform mode at room temperature at 200.13 MHz and 50.32 MHz respectively. The samples were dissolved in CDCl₃, CD₂Cl₂ or C₆D₆. As reference the residual peak of CHCl₃ or CHDCl₂ or C₆HD₅ in the ¹H spectra (7.25 ppm, 5.35 ppm and 7.15 ppm, respectively) and the peak of the solvent in the ¹³C spectra (77.00 ppm for CDCl₃) were used. Proton spectra were acquired with a 15° pulse and 2 seconds of delay between pulses; 32 transients were stored for each spectrum. The carbon spectra were acquired with a 45° pulse and 6 seconds of delay between pulses; about 512 transients were stored for each spectrum. CDCl₃ (Aldrich, 99.8 atom % D) and C₆D₆ (Aldrich, 99.6 atom % D) were stored under molecular sieves (4–5 Å), while CD₂Cl₂ (Aldrich, 99.8 atom % D) was used as received.

Preparation of the samples was carried out under nitrogen using standard inert atmosphere techniques.

The proton and carbon spectra of polymers were obtained using a Bruker DPX 400 spectrometer operating in the Fourier transform mode at 120° C. at 400.13 MHz and 100.61 MHz respectively. The samples were dissolved in C₂D₂Cl₄. As reference the residual peak of C₂DHCl₄ in the ¹H spectra (5.95 ppm) and the peak of the mmmm pentad in the ¹³C spectra (21.8 ppm) were used. Proton spectra were acquired with a 450 pulse and 5 seconds of delay between pulses; 256 transients were stored for each spectrum. The carbon spectra were acquired with a 90° pulse and 12 seconds (15 seconds for ethylene based polymers) of delay between pulses and CPD (waltz 16) to remove ¹H-¹³C couplings. About 3000 transients were stored for each spectrum.

GC-MS analyses were carried out on a HP 5890—serie 2 gas-chromatograph and a BP 5989B quadrupole mass spectrometer.

The intrinsic viscosity (I.V.) was measured in tetrahydronaphtalene (THN) at 135° C.

The melting points of the polymers (T_(m)) were measured by Differential Scanning Calorimetry (D.S.C.) on an Perkin Elmer DSC-7 instrument, according to the standard method. A weighted sample (5–10 mg) obtained from the polymerization was sealed into aluminum pans and heated at 200° C. with a scanning speed corresponding to 20° C./minute. The sample was kept at 200° C. for 5 minutes to allow a complete melting of all the crystallites. Successively, after cooling to 0° C. with a scanning speed corresponding to 20° C./minute, the peak temperature was taken as crystallization temperature (T_(c)). After standing 5 minutes at 0° C., the sample was heated for the second time at 200° C. with a scanning speed corresponding to 20° C./min. In this second heating run, the peak temperature was taken as the melting temperature (T_(m)) and the area as global melting enthalpy (ΔH_(f)).

The molecular weight distribution was determined by SEC on a WATERS 200 machine in trichlorobenzene at 135° C.

The following abbreviations are used:

-   aq.=aqueous -   THF=tetrahydrofuran -   Et₂O=diethyl ether -   CH₂Cl₂=dichloromethane -   DMF=N,N-dimethylformamide -   Me₂SiCl₂=dichlorodimethylsilane -   Me₃SiCl=chlorotrimethylsilane -   CuCl₂=copper (II) chloride -   POCl₃=phosphorus oxychloride -   B(OMe)₃=trimethyl borate -   AlCl₃=aluminium trichloride -   n-BuLi=normal butyllithium -   Dppf=diphenylphosphinoferrocene -   TMEDA=N,N,N′,N′-tetramethylethylenediamine -   ZrCl₄=zirconium tetrachloride -   HfCl₄=hafnium chloride -   Th₂Cp=7H-cyclopenta[1,2-b:4,3-b′]-dithiophene or     7H-thieno[3′,2′:3,4]-cyclopenta[b]thiophene -   MeTh₂Cp=2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene -   EtTh₂Cp=2,5-diethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene -   PhTh₂Cp=2,5-diphenyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene -   AcOH=acetic acid -   (MeO)²CH₂=dimethoxymethane

Preparation of the Ligand Precursors Synthesis of 3,3′-dibromo-2,2′-dithienylmethanol

A 2.5 M solution of n-BuLi in hexane (24.30 mL, 60.76 mmol) was added dropwise at −20° C. to a solution of 15.00 g of 2,3-dibromothiophene (Aldrich, 98%, Mw=241.94, d=2.137, 60.76 mmol, n-BuLi:2,3-Br₂thiophene=1:1) in 90 mL of ether. The solution turned from pale yellow to yellow. After 1 h stirring at −20° C., 2.53 mL of ethylformate (Aldrich, 97%, Mw=74.08, d=0.917, 30.38 mmol, HCOOEt:2,3-Br₂thiophene=0.5:1) in 30 mL of ether was added dropwise. During the addition the solution turned from yellow to dark yellow. The reaction mixture was kept at −20° C. for 15 min, then allowed to warm to room temperature and stirred for 20 h. The final pale orange suspension was poured at 0° C. into acidic water (1.65 g of NH₄Cl in 75 mL of water), the organic layer was separated out and the water layer extracted with ether (3×25 mL). The organic layers were collected, dried over Na₂SO₄ and the solvents were removed under vacuum at 30–35° C. to give an orange oil (9.52 g), which was characterized by GC-MS analysis and ¹H-NMR spectroscopy.

Purity (by GC-MS)=96.0%. Yield of the pure product=85.0%. ¹H NMR (δ, ppm, CDCl₃): 7.28 (d, 2H, J=5.29 Hz, CH); 6.95 (d, 2H, J=5.29 Hz, CH); 6.41 (s, 1H, CH); 2.86 (bs, 1H, CH). m/z (%): 356 (23) [M⁺+4], 354 (42) [M⁺+2], 352 (22) [M⁺], 339 (10), 337 (18), 275 (10), 273 (10), 194 (11), 193 (23), 192 (11), 191 (100), 177 (32), 166 (10), 164 (10), 121 (17), 111 (14), 84 (33), 83 (15), 82 (26), 81 (14), 69 (11), 45 (33), 39 (15).

Synthesis of 3,3′-dibromo-2,2′-dithienylmethane

9.45 g of 3,3′-dibromo-2,2′-dithienylmethanol obtained as described above (Nw=354.09, 26.69 mmol considering starting material as 100% pure) were dissolved in 85 mL of dichloromethane in a 250 mL three-necked bottom flask under nitrogen atmosphere and 4.26 mL of triethylsilane (Aldrich, Mw=116.28, d=0.728, 26.69 mmol) were added at 0° C. Then 2.06 mL of CF₃COOH (Aldrich, Mw=114.02, d=1.48, 26.69 mmol) were added dropwise at 0° C. to the stirred mixture. During the addition, the reaction mixture turned from dark orange to dark red. It was kept at 0° C. for 15–20 min, then allowed to warm to room temperature and stirred for 3 h and 30 min at the same temperature. After cooling to 0° C., potassium carbonate (Fluka, 3.69 g, Mw=138.21, 26.69 mmol) was added to the dark red solution, and the resulting mixture was stirred for 30 min at room temperature and finally filtered on G4 fit. The residue on the frit was washed twice with CH₂Cl₂ (2×20 mL) until colourless, while the filtrate was dried under vacuum at 45° C. for 3 h to give a dark red oil (9.07 g), which was analysed by GC-MS analysis and ¹H-NMR spectroscopy. Purity (by GC-MS)=79.9%. Yield of the pure product=80.3%. 3-bromo-2,2′-dithienylmethane (9.9 wt %.) and hexaethyldisiloxane (6.2 wt %.) were present as by-products. The product was used as such in the next step without further purification.

¹H NMR (Δ, ppm, CDCl₃): 7.16 (d, 2H, J=5.38 Hz, CH); 6.94 (d, 2H, J=5.38 Hz, CH); 427 (s, 2H, CH₂). m/z (%): 340 (28) [M⁺+4], 338 (51) [M⁺+2], 336 (26) [M⁺], 259 (55), 257 (51), 179 (15), 178 (100), 177 (43), 89 (16), 45 (10).

Synthesis of 7H-cyclopenta[1,2-b:4,3-b′]dithiophene

A 2.5 M solution of n-BuLi in hexane (21.30 mL, 53.25 mmol) was added dropwise at −50° C. to a solution of 8.99 g of 3,3′-dibromo-2,2′-dithienylmethane obtained as described above (Mw=338.09, 26.59 mmol) in 75 mL of ether under nitrogen atmosphere in a 250 mL flask. After 1 h stirring at −50° C., the dark brown dilithium suspension was added slowly to a suspension of 7.26 g of CuCl₂ (Aldrich, 98%, Mw=134.45, 52.92 mmol) in 50 mL of Et₂O. The reaction mixture was kept at −50° C. for 30 min, allowed to warm to −20° C. in 2 h 30 min and then allowed to reach 0° C. in few minutes. Aliquots were taken after 30 min at −50° C., at −20° C. and after 1 h at −0° C. to follow the reaction state by GC-MS analysis. It appeared that the CuCl₂ induced coupling reaction starts at −50° C. but proceeds slowly until 0° C. Only 10 wt % of 7H-cyclopenta[2,1-b:4,3-b′]dithiophene was formed after 1 h at 0° C. After keeping at 0° C. for 1 h 30 min, the reaction mixture was stirred overnight at room temperature and subsequently poured at 0° C. into 100 mL of an aqueous 2 M HCl solution. The resulting mixture was stirred for 15 min at room temperature, filtered in order to remove the greyish precipitate of Cu₂Cl₂, the ether layer was separated and the aqueous phase extracted with ether. The combined ethereal extracts were washed with HCl 2 M (100 mL), twice with NaHCO₃ aq. and finally with ether. The resulting organic phase (final volume=300 mL) was dried with Na₂SO₄ and the solvents removed in vacuo giving 3.16 g of a dark red oil, which was analysed by GC-MS analysis and ¹H-NMR spectroscopy. The analysis showed the presence of the desired product together with dimers, trimers and tars. The crude product was added of 40 mL of ethanol and stirred for 1 h at room temperature. The yellow-orange extract was concentrated in vacuo at 55° C. for 4 h to give a dark orange oil (1.92 g), which crystallized by standing at 0° C. overnight.

Purity (by GC-MS)=ca. 50%. Yield of the pure product=20.2%. ¹H NMR (δ, ppm, CDCl₃): 7.30 (d, 2H, J=4.93 Hz, CH); 7.13 (d, 2H, J=4.93 Hz, CH); 3.80 (s, 2H, CH₂). m/z (%): 180 (9) [M⁺+2], 179 (16) [M⁺+1], 178 (100) [M⁺], 177 (92), 134 (13), 89 (7), 69 (6), 45 (6).

Synthesis of bis(3,5-dibromo2-thienyl)methanol (or 3,3′,5,5′-tetrabromo-2,2′-dithienyl carbinol)

A solution of 31.35 g of 2,3,5-tribromothiophene (Lancaster, 98%, MW=320.84, 95.75 mmol) in 70 mL of ether was cooled to −78° C. and 38.3 mL of a 2.5 M n-BuLi solution in hexane (95.75 mmol) were added dropwise. The resulting mixture was allowed to warm to room temperature, stirred in additional 1 h and then added at 0° C.÷−10° C. to a solution of 3.86 mL of ethylformate (Aldrich, 97%, MW=74.08, d 0.917, 46.35 mmol) in 20 mL of hexane, previously cooled to 0° C.÷−10°0 C. At the end of the addition (˜20 min) the reaction mixture was allowed to warm to room temperature and then refluxed for 1 h. The resulting mixture was quenched with 7.5 mL of water, the organic layer was separated out, dried over magnesium sulphate and the solvents evaporated off giving 23.2 g of a pale brown solid, which was analyzed by ¹H NMR, ¹³C NMR, GC-MS. Purity=93.0%. Isolated yield with respect to ethylformate=90.9%.

¹H NMR (δ in ppm, CDCl₃): 6.92 (s, 2H, CH); 6.26 (d, 1H, CH bridge, J=3.2 Hz); 2.73 (d, 1H, OH, J=3.2 Hz) ¹³C NMR (δ in ppm, CDCl₃): 67.38 (CHOH), 108.60, 113.58, 132.18 (CH), 141.10. m/z (%): 512 (67) [M⁺], 494 (50), 433 (54), 352 (53), 335 (35), 285 (43), 269 (100), 242 (19), 162 (33), 81 (27), 39 (13).

Synthesis of 3,3′,5,5′-tetrabromo-2,2′-dithienylmethane

Trifluoroacetic acid (0.25 mL, Aldrich, 99%, MW=114.02, d=1.48, 3.24 mmol) was added at room temperature to a solution of 1.75 g of bis(3,5-dibromo-2-thienyl)methanol (93.0%, MW=511.90, 3.18 mmol) in 15 mL of methylene chloride containing 0.50 mL of triethylsilane (Aldrich, 99%, MW=116.28, d=0.728, 3.13 mmol). The resulting red solution was stirred for 1 h at room temperature, neutralized with solid potassium carbonate (0.4 g, MW=138.21, 2.89 mmol), filtered and evaporated off to give a pale red solid. Yield of crude product=100%.

¹H NMR (δ in ppm, CDCl₃): 6.94 (s, 2H, CH); 4.17 (s, 2H, CH₂). ¹³C NMR (δ in ppm, CDCl₃): 29.30 (CH₂), 109.07, 111.38, 131.98 (CH), 137.22. m/z (%): 496 (71) [M⁺+4], 417 (76)[M⁺], 336 (91), 255 (100), 176 (41), 125 (46), 95 (30), 69 (40), 45 (22).

Synthesis of 3,3′-dibromo-5,5′-dimethyl-2,2′-dithienylmethane

A precooled (−20° C.) 2.5 M solution of n-BuLi in hexane (41.1 mL, 102.75 mmol) was added at −20° C. to a solution of 25.48 g of 3,3′,5,5′-tetrabromo-2,2′-dithienylmethane (MW=495.90, 51.38 mmol) in 100 mL of Et₂O. After 30 min stirring at −20° C., a precooled (−20° C.) ethereal (10 mL) solution of dimethyl sulphate (Aldrich, 9.72 mL, MW=126.13, d=1.333, 102.75 mmol) was added. The resulting black suspension was stirred for 45 min at −20° C.; the cooling bath was then removed and the flow of nitrogen stopped. A 4 N solution of sodium hydroxide (2.5 mL, 10 mmol) was added and the mixture vigorously stirred for 2 h at room temperature. The resulting reaction mixture was dried by magnesium sulphate, filtered, the residue on the frit washed twice with ether (to recover all the product) and the filtrate was concentrated under reduced pressure at 40° C. for 2 h giving 17.8 g of a brown solid. Purity=87.8% (by GC-MS). Yield of pure product=83.1% (crude yield=94.6%).

¹H NMR (δ in ppm, CDCl₃): 6.58 (q, 2H, CH, J=1.0 Hz); 4.11 (s, 2H, CH₂); 2.39 (d, 6H, CH₃, J=1.0 Hz). ¹³C NMR (δ in ppm, CDCl₃): 15.41 (CH₃), 28.88 (CH₂), 108.20, 127.57 (CH), 134.10, 138.70. m/z (%): 366 (43) [M⁺], 287 (47), 206 (100), 191 (21), 173 (14), 103 (10), 59 (20).

Synthesis of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene (or 2,5-dimethyl-7H-thieno[3′,2′:3,4]cyclopenta[b]thiophene)

A precooled (−70° C.) 2.5 M n-BuLi solution in hexane (27.1 mL, 67.75 mmol) was added dropwise at −70° C. to a solution of 10.77 g of 3,3′-dibromo-5,5′-dimethyl-2,2′-dithienylmethane NW=366.15, 29.41 mmol) in 60 mL of ether. At the end of the addition, the brown suspension was stirred for additional 30 min at the same temperature. Then a precooled (−70° C.) suspension of 10.28 g of CuCl₂ anhydrous (dried at 130° C. for 1 h, MW=134.45, 76.46 mmol) in 35 mL of ether was added quickly. The resulting black suspension was kept at −70° C. for 10 min, at −50° C. for 1 h, at −20° C. for 1 h and at 0° C. for 1 h. Then it was allowed to warm to room temperature and stirred overnight. The colour of the reaction mixture was changed from black to pale brown by increasing the temperature. Aliquots were taken during the reaction for the GC-MS analysis: at −50° C. titre of the desired compound=8.6%, at −20° C. title in the desired compound=20.9%, at 0° C. title in the desired compound=68.8%. The final suspension was poured into 160 mL of an ammonium chloride saturated aqueous solution, the organic layer was separated, the water layer washed with ether, the organic layers collected and dried. 4.79 g of a black solid was obtained. Purity (by GC-MS)=75.9%. Yield of pure product=60.0% (crude yield=79.0%).

¹H NMR (δ in ppm, CDCl₃): 6.78 (s, 2H, CH); 3.69 (s, 2H, CH₂); 2.54 (s, 6H, CH₃) ¹³C NMR (δ in ppm, CDCl₃): 15.96 (CH₃), 33.13 (CH₂), 116.43 (CH), 140.16, 142.16, 143.67. m/z (%): 206 (100) [M⁺], 191 (54), 173 (29), 158 (6), 147 (8).

Synthesis of 3,3′-dibromo-5,5′-ditrimethylsilyl-2,2′-dithienylmethane

A 2.18 M solution of n-BuLi (65 mL, 141.7 mmol) was added at −70° C. to a solution of 34.8 g of 3,3′,5,5′-tetrabromo-2,2′-dithienylmethane (70.2 mmol) in 150 mL of ether. The mixture was stirred for 30 min at the same temperature and 35.5 mL of Me₃SiCl (280 mmol) in 65 mL of ether were then added. The resulting mixture was allowed to warm to room temperature, the LiCl was filtered off, and the mother solution was evaporated off to give an oil which represented the target compound in at least 95% purity. To this oil 50 mL of hexane was added and the resulting solution kept at −30° C. for 10 h. Large crystals were isolated, washed with cooled hexane and dried. Yield of recrystallized product 60%. The title compound was characterized by ¹H-NMR and ¹³C-NMR spectroscopy.

Synthesis of 2,5-ditrimethylsilyl-7H-cyclopenta[1,2b:4,3-b′]dithiophene (or 2,5-dimethyltrimethylsilyl-7H-thieno[3′,2′:3,4]cyclopenta[b]thiophene)

A solution of 0.1 mol of 3,3′-dibromo-5,5′-ditrimethylsilyl-2,2′-dithienylmethane in 200 mL ether was treated with 0.23 mol of n-BuLi at −70° C. At the end of the addition, the reaction mixture was stirred for additional 30 min at the same temperature. Then 0.265 mol of CuCl₂ was added quickly. The resulting mixture was allowed to warm to room temperature and stirred overnight. The resulting suspension was poured into water, the organic phase was separated and concentrated. The residue was passed through a column packed with SiO₂ using hexane or a hexane/ether mixture as eluent. The resulting solution was evaporated off giving a crystalline or oily-crystalline solid which represented the desired product. Yield 50–60%. The crude product can be further purified in ether by filtration at 0° C. or by recrystallization from pentane. The title compound was characterized by ¹H-NMR and¹³C-NMR spectroscopy.

Synthesis of 3,3′-dibromo-5,5′-dihydroxyboryl-2,2′-dithienylmethane

A 1.6 N solution of n-BuLi (100 ml, 160 mmol) was added to a solution of 39.6 g of 3,3′,5,5′ -tetrabromo-2,2′-dithienylmethane (79.8 mmol) in 150 mL ether at −70° C. The mixture was stirred for 30 min at the same temperature and 23.3 g of B(OMe)₃ (220 mmol) in 100 mL of ether were then added. The reaction mixture was allowed to warm to room temperature. The resulting suspension was treated with 100 mL of a 10% aqueous HCl solution, the organic layer was separated, washed twice with 50 mL of a aqueous Na₂CO₃ 10% solution, evaporated off and dried. The resulting solid which represented the crude di-boronic acid was used in the next step without further purification. The title compound was characterized by ¹H-NMR and ¹³C-NMR spectroscopy.

Synthesis of 3,3′-dibromo-5,5′-diphenyl-2,2′-dithienylmethane

1.81 g of 3,3′-dibromo-5,5′-dihydroxyboryl-2,2′-dithienylmethane (3.76 mmol) 1.40 g of PhI (6.84 mmol), 0.15 g of PdCl₂(dppf)₂ (0.21 mmol), 120 mL of DMF and 8 mL of Et₃N were placed into a reaction flask and this mixture was stirred at 80° C. for 2 h. The resulting mixture was poured into a CH₂Cl₂/water two-phase system. The organic layer was collected, washed twice with 30 mL of 10% phosphoric acid, then with water and finally evaporated off. The residue was passed through a column packed with SiO₂ using hexane/CH₂Cl₂=1/1 as eluent. The resulting solution was evaporated off, the residue washed with hexane and dried to give 0.6 g of diphenyl derivative. Yield 32%. The title compound was characterized by ¹H-NMR and ¹³C-NMR spectroscopy.

Synthesis of 2,5-diphenyl-7H-cyclopenta[1,2b:4,3b′]dithiophene (or 2,5-diphenyl -7H-thieno[3′,2′:3,4]cyclopenta[b]thiophene) Example 30 Synthesis of 1-bromo-2-(3-indenyl)ethane

A 1.6 M n-BuLi solution in hexane (100 mL, 0.16 mol) was added at 0° C. to a solution of indene (18.6 g, MW=116.16, 0.16 mol) in 300 mL of ether. The resulting suspension was allowed to warm to room temperature and stirred for 4 h at the same temperature. Then the indenyl lithium suspension was cooled again to −50° C. and added of a solution of 1,2-dibromoethane (0.24 mol, 21 mL) in 50 mL of ether. The reaction mixture was allowed to warm up slowly to room temperature and stirred overnight. Then it was treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated, evaporated off to dryness and distilled in vacuo, b.p. 110° C./0.5 torr. Yield 21.6 g (60%). The title compound was characterized by NMR spectroscopy.

Synthesis of 1,2-(3-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)ethane

A solution of 2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene (1.03 g, 5 mmol) in 50 mL of THF was treated at −70°C. with a 1.6 M n-BuLi solution in hexane (3.1 mL, 5 mmol). The resulting mixture was stirred for additional 45 min at 0° C., then cooled again to −70° C. and treated with 1-bromo-2-(3-indenyl)ethane (1.12 g, 5 mmol) in 25 mL of THF. The reaction mixture was allowed to warm to room temperature and subsequently treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated and the solvents were removed. The residue was passed through a column packed with silica gel by using hexane as eluent. Yield 1.26 g (72%). The title compound was characterized by NMR spectroscopy.

Synthesis of ethylidene{(1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-37

¹H NMR (δ in ppm, CDCl₃): 6.99 (d, 1H, H_(α)); 6.69 (q, 1H, H_(β)); 2.48 (d, 3H, CH₃).

Synthesis of 2-methyl-4-formyl-thiophene

A 1.6 M solution of n-BuLi (164 mL, 0.26 mol) was added at −70° C. to a stirred solution of 44.26 g of 2-methyl-4-bromo-thiophene (0.25 mol) in 300 mL of ether. The resulting solution was kept under stirring at −60° C. to −70° C. for 30 min and then was treated with 27.4 g of dimethylformamide (0.37 mol) in 100 mL of ether. The mixture was allowed to warm to room temperature, then neutralized with 10% aqueous solution of NH₄Cl, washed with 10% aqueous solution of H₃PO₄ and finally with water up to neutral pH. The organic phase was collected, evaporated off and distilled at 110° C./10 mmHg. Yield 22.3 g (71%). The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of 2,2′-dimethyl-4,4′-dithienylmethane

113 mL of 1.6 M n-BuLi solution (0.18 mol) was added to a solution of 31.3 g of 2-methyl-4-bromo-thiophene (0.177 mol) in 150 mL of ether at −70° C. under stirring. The resulting solution was kept under stirring at −60 to −70° C. for 30 min and then was added of 22.3 g of 2-methyl-4-formyl-thiophene (0.177 mol) in 100 mL of ether. The mixture was allowed to warm to room temperature, then neutralized with 10% aqueous solution of NH₄Cl and washed with water. The organic phase was separated and evaporated. The crude bis(2-methyl-4-thienyl)methanol (or 2,2′-dimethyl-4,4′-dithienyl carbinol) was obtained.

A suspension of 35.5 g of AlCl₃ (0.266 mol) in 100 mL of ether was added slowly to a suspension of 10 g of LiAlH₄ (0.266 mol) in 100 mL of ether. The resulting mixture was treated with the solution of the carbinol (obtained as described above) in 100 mL ether. The reaction mixture was refluxed for additional 1 h, cooled to room temperature and subsequently added of 100 mL of ethyl acetate. Then it was treated with 300 mL of water and 300 mL of ether. The organic phase was collected, washed with water, dried by MgSO₄ and evaporated off. The residue was distilled at 90 to 110° C./0.5 mmHg. Yield 23.2 g (63%). The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of 2,6-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene (or 2,6-dimethyl-4H-thieno[3′,2′:2,3]cyclopenta[b]thiophene)

1.04 g of 2,2′-dimethyl-4,4′-dithienylmethane (5 mmol) was dissolved in 30 mL of ether and added of 9 mL of a 1.6 M solution of n-BuLi (14.4 mmol) and of 1.74 g of TMEDA (15 mmol) at −70° C. under stirring. The resulting mixture was allowed to warm to room temperature, stirred for 1 h, then cooled again to −70° C. and treated with 2.7 g of CuCl₂ (20 mmol). The resulting reaction mixture was allowed to warm to room temperature and added of 30 mL of water. The organic phase was collected and passed through a column packed with silica gel. The resulting solution was evaporated off to give 0.34 g of the product. Yield 34%. The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of 2-ethyl-4-bromo-thiophene

1 mol of acethylthiophene dissolved in 250 mL of CHCl₃ was added slowly to a suspension of 2.5 mol of AlCl₃ in 1000 mL of CHCl₃ under stirring keeping the temperature below 40° C. At the end of the addition, 1.2 mol of Br₂ was carefully added dropwise under stirring. The resulting mixture was stirred overnight and then was poured into a mixture of ice (0.5 Kg) and hydrochloric acid (100 mL, 32%). The organic phase was isolated and the solvent was removed. The resulting substance was dissolved in 700 mL of diethyleneglicole and the so-obtained solution was treated with 5.5 mol of 100% hydrazine hydrate. The resulting mixture was refluxed for 30 min. After cooling to room temperature, 2.75 mol of KOH were added. When the gas evolution was ended, the product was distilled. The fraction under the temperature of 150° C. was collected. This fraction represented a mixture of water and product. The organic layer was collected and distilled at 80° C./10 torr. Yield 45%.

¹H-NMR (δ, ppm, CDCl₃): 7.05 (d, 1H, H5); 6.76 (q, 1H, H3); 2.86 (q, 2H, CH₂); 1.33 (t, 3H, CH₃).

Synthesis of 3,3′-dibromo-5,5′-diethyl-2,2′-dithienylmethane

The 2-ethyl-4-bromo-thiophene obtained in the previous step was dissolved into 120 mL of AcOH and was treated with a mixture of 6.1 mL of H₂SO₄ and 9.1 mL (MeO)₂CH₂. The reaction mixture was stirred overnight, then was washed with 300 mL of water and finally extracted with CH₂Cl₂. The organic phase was separated and dried under reduced pressure. The residue was passed through a column packed with Al₂O₃ using hexane as eluent. The solvent was removed and the desired product was obtained as yellow oil. Yield 90%.

¹H-NMR (δ, ppm, CDCl₃): 6.68 (m, 2H, CH); 4.20 (s, 2H, CH₂ bridge); 2.80 (q, 4H, CH₂); 1.30 (t, 6H, CH₃).

Synthesis of 2,5-diethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene

A solution of 0.1 mol of 3,3′-dibromo-5,5′-diethyl-2,2′-dithienylmethane in 200 mL of ether was treated at −70° C. with 0.23 mol of n-BuLi. At the end of the addition, the mixture was stirred for additional 30 min at the same temperature. The white precipitate of the dilithium salt was formed. Then 0.265 mol of CuCl₂ was added quickly at −70° C. The reaction mixture was allowed to warm to room temperature and stirred for 12 h. The resulting suspension was poured into water, the organic phase was separated and concentrated. The residue was recrystallized from ether. Yield 25%.

¹H-NMR (δ, ppm, CDCl₃): 6.86 (m, 2H, CH); 3.74 (s, 2H, CH₂); 2.98 (q, 4H, CH₂); 138 (t, 6H, CH₃).

Example 1 Synthesis of 2,2-(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b′]-dithiophene)propane

3.13 mL of a 1.6 M solution of n-BuLi (5 mmol) was added at −70° C. to a solution of 1.03 g (5 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 20 mL of ether. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.6 g (5 mmol) of 3,6,6-trimethylfulvene in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and then treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated, dried by MgSO₄ and concentrated. The residue was recrystallized from hexane. Yield 1.0 g (62%). The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of isopropylidene{(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-1

2.3 mL of 1.6 M n-BuLi solution (3.7 mmol) was added at −70° C. to a suspension of 0.6 g (1.85 mmol) of 2,2-(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)propane in 20 mL of ether. The mixture was allowed to warm to 0° C. and then was treated with 0.43 g (1.85 mmol) of ZrCl₄. The reaction mixture was refluxed under stirring for 3 h, then the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 0.72 g (80%). The title compound was characterized by ¹H-NMR spectroscopy.

Example 2 Synthesis of isopropylidene{(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}hafnium dichloride CH-1

2.5 mL of 1.6 M n-BuLi solution (4.0 mmol) was added at −70° C. to a suspension of 0.65 g (2.0 mmol) of 2,2-(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)propane in 20 mL of ether. The mixture was allowed to warm to 0° C. and then was treated with 0.64 g (2.0 mmol) of HfCl₄. The reaction mixture was refluxed under stirring for 3 h, then the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 0.48 g (42%). The title compound was characterized by ¹H-NMR spectroscopy.

Example 3 Synthesis of 2,2-(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta [1,2-b:43b′]-dithiophene)propane

The same procedure described for the synthesis of 2,2-(3-methyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b′]-dithiophene)propane was followed (see below).

Synthesis of isopropylidene{(2,4-dimethyl-cyclopentadienyl)7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-12

3.13 ml of 1.6 M n-BuLi solution (5.0 mmol) was added at −70° C. to a solution of 1.03 g (5.0 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene in 20 mL of ether. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.67 g (5.0 mmol) of 1,3,6,6-tetramethylfulvene in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and stirred for 8 h. Successively, it was cooled to −30° C. to add 3.13 mL of 1.6 M n-BuLi solution (5.0 mmol). The mixture was then allowed to warm to 0° C. and treated with 1.16 g (5.0 mmol) of ZrCl₄. The reaction mixture was refluxed under stirring for 3 h and 10 mL of CH₂Cl₂ was added at room temperature. The solution was isolated, concentrated and the residue was recrystallized from CH₂Cl₂/hexane. Yield 0.58 g (23% based on 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene).

Example 4 Synthesis of 2,2-(3-isopropyl-cyclopentadienyl-7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b′]-dithiophene)propane

3.13 mL of a 1.6 M solution of n-BuLi (5 mmol) was added at −70° C. to a solution of 1.03 g (5 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 20 mL of ether. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.74 g (5 mmol) of 3-isopropyl-6,6-dimethylfulvene in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and then treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated, dried by MgSO₄ and concentrated. The residue was recrystallized from hexane. Yield 0.85 g (48%). The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of isopropylidene{(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-2

3.75 mL of 1.6 M n-BuLi solution (6.0 mmol) was added at −70° C. to a suspension of 1.06 g (3.0 mmol) of 2,2-(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)propane in 20 mL of ether. The mixture was allowed to warm to 0° C. and then was treated with 0.7 g (3.0 mmol) of ZrCl₄. The reaction mixture was refluxed under stirring for 3 h, then the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.24 g (80%). The title compound was characterized. by ¹H-NMR spectroscopy.

Example 5 Synthesis of 2,2-(3-isopropyl-cyclopentadienyl)-7-(2,5-ditrimethylsilyl-cyclopenta [1,2-b:4,3-b′]-dithiophene)propane

The same procedure as described in Example 4 for 2,2-(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)propane was followed excepting that 2,5-ditrimethylsilyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene (or 2,5-dimethyltrimethylsilyl-7H-thieno[3′,2′:3,4]cyclopenta[b]thiophene) was used (see below).

Synthesis of isopropylidene{(3-isopropyl-cyclopentadienyl)-7-(2,5-ditrimethylsilyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-7

3.05 mL of 1.6 M n-BuLi solution (4.9 mmol) was added at −70° C. to a solution of 1.57 g (4.86 mmol) of 2,5-ditrimethylsilyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene in 20 mL ether. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.72 g (4.9 mmol) of 3-isopropyl-6,6-dimethylfulvene in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and stirred for 4 h. Successively, it was cooled to −30° C. to add 3.05 mL of 1.6 M n-BuLi solution (4.9 mmol). The mixture was allowed to warm to 0° C. and treated with 1.14 g (4.9 mmol) of ZrCl₄. The resulting reaction mixture was refluxed under stirring for 3 h, then the solution was isolated and concentrated. The residue was recrystallized from pentane. Yield 0.23 g (7.4% based on 2,5-ditrimethylsilyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene). The title compound was characterized by ¹H-NMR spectroscopy.

Example 6 Synthesis of 2,2-(3-isopropyl-cyclopentadienyl)-4-(2,6-dimethyl-cyclopenta[2,1-b:394-b′]dithiophene)propane

The same procedure as described in Example 4 was followed, excepting that 2,6-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene was used (see below).

Synthesis of isopropylidene{(3-isopropyl-cyclopentadienyl)-4-(2,6-dimethyl-cyclopenta[2,1-b:3,4-b′]-dithiophene)}zirconium dichloride C-8

3.13 mL of 1.6 M n-BuLi solution (5.0 mmol) was added at −70° C. to a solution of 1.03 g (5.0 mmol) of 2,6-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene in 20 mL of ether. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.74 g (5.0 mmol) of 3-isopropyl-6,6-dimethylfulvene in 10 mL of ether. The mixture was allowed to warm to room temperature and stirred for 4 h. Successively, it was cooled to −30° C. to add 3.13 mL of 1.6 M n-BuLi solution (5.0 mmol). The reaction mixture was allowed to warm to 0° C. and treated with 1.16 g (5.0 mmol) of ZrCl₄. The resulting reaction mixture was refluxed under stirring for 3 h and subsequently 30 mL of CH₂Cl₂ was added at room temperature. The solution was isolated and concentrated. The residue was recrystallized from CH₂Cl₂/hexane. Yield 0.87 g (34% based on 2,6-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene). The title compound was characterized by ¹H-NMR spectroscopy.

Example 7 Synthesis of 2,2-(3-tert-butyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b′]-dithiophene)propane

3.13 mL of a 1.6 M solution of n-BuLi (5 mmol) was added at-70° C. to a solution of 1.03 g (5 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 20 mL of ether. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.81 g (5 mmol) of 3-tert-butyl-6,6-dimethylfulvene in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and then treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated, dried by MgSO₄ and concentrated. The residue was recrystallized from hexane. Yield 0.94 g (51%). The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of isopropylidene{(3-tert-butyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-3

3.75 mL of 1.6 M n-BuLi solution (6.0 mmol) was added at −70° C. to a suspension of 1.11 g (3.0 mmol) of 2,2-(3-tert-butyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)propane in 20 mL of ether. The mixture was allowed to warm to 0° C. and treated with 0.7 g (3.0 mmol) of ZrCl₄. The reaction mixture was refluxed under stirring for 3 h, then the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.27 g (80%). The title compound was characterized by ¹H-NMR spectroscopy.

Example 8 Synthesis of 2,2(3-isopropyl-cyclopentadienyl)-7-(cyclopenta [1,2-b:4,3-b′]-dithiophene)propane

3.13 mL of 1.6 M solution of n-BuLi (5 mmol) was added to a solution of 0.89 g (5 mmol) of 7H-cyclopenta[1,2-b:4,3-b′]dithiophene in 20 mL of THF at −70° C. The resulting mixture was stirred for additional 30 min at 0° C., then cooled again to −70° C. and treated with 0.74 g (5 mmol) of 3-isopropyl-6,6-dimethylfulvene in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and then treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated, dried by MgSO₄ and concentrated. The residue was passed through a column packed with silica gel using hexane as eluent (R_(f)=0.8). Yield 1.05 g(64%). The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of isopropylidene(3-isopropyl-cyclopentadienyl)-7-(cyclopenta[1,2-b:4,3-b′]-dithiophene) zirconium dichloride C-16

A solution of 1.05 g (3.22 mmol) of 2,2-(3-isopropyl-cyclopentadienyl)-7-(cyclopenta [1,2-b:4,3-b′]-dithiophene)propane in a mixture of 10 mL of ether and 60 mL of hexane was treated at −70° C. with 4.1 mL (6.6 mmol) of a 1.6 M n-BuLi solution. The mixture was allowed to warm to 0° C. and treated with 0.75 g (3.2 mmol) of ZrCl₄. The resulting reaction mixture was reflexed under stirring for 3 h, then the yellow precipitate was filtered, washed twice with hexane, dried and finally recrystallized from CH₂Cl₂/hexane. Yield 0.32 g (21%). The title compound was characterized by ¹H-NMR spectroscopy.

Example 9 Synthesis of isopropylidene{(cyclopentadienyl)-7-(cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-0

It was carried out as described in the Example 6 of WO 98/22486.

Example 10 Synthesis of chloro(1-indenyl)dimethylsilane

37.5 mL of a 2.5 M solution of n-BuLi in hexane (93.75 mmol, n-BuLi:indene=1.1:1) was added dropwise to a solution of indene purity 90%, 11 g, 85.23 mmol) in 60 mL of Et₂O, previously cooled to −78° C. At the end of the addition, the yellow slurry was allowed to reach room temperature and stirred for 4 hours to give an orange solution. The solvents were evaporated off under reduced pressure to give a yellow solid, which was taken up in 75 mL of hexane; the milky suspension was stirred for few minutes and the lithium salt of indene (white precipitate) was filtered and washed with hexane (3×20 mL). The solid was again slurried in hexane (40 mL) and added to a stirred solution of Me₂SiCl₂ (15.5 mL, 127.84 mmol, Me₂SiCl₂/IndLi=1.5:1) in 50 mL of hexane, previously cooled to −78° C. At the end of the addition, the mixture was allowed to reach room temperature and stirred overnight. The suspension was then filtered, and the filtrate brought to dryness in vacuum to yield a pale yellow oil (16.5 g) of (1-Ind)SiMe₂Cl free from its vinylic isomer (yield 89%).

¹H NMR (□ in ppm, CDCl₃): 0.21 (s, 3H, Si—CH₃), 0.26 (s, 3H, Si—CH₃), 3.77 (bs, 1H, Cp-H), 6.68 (dd, 1H, Cp-H), 7.03 (dd, 1H, Cp-H), 7.19–7.36 (m, 2H, Ar), 7.48–7.52 (m, 1H, Ar), 7.57–7.61 (m, 1H, Ar).

Synthesis of (1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene) dimethylsilane

A 2.5 M solution of n-BuLi in hexane (4.80 mL, 12.00 mmol) was added at −20° C. to a suspension of 2.25 g of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene (Mw=206.32, 10.90 mmol, n-BuLi: MeTh₂Cp=1.1:1) in 50 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. with final formation of a dark brown suspension. This suspension was cooled again to −20° C. and added of a solution of 2.20 g of chloro(1-indenyl)dimethylsilane (Mw=208.76, 10.54 mmol, IndSiMe₂Cl:MeTh₂Cp=1:1) in 10 mL of ether. The reaction mixture was then allowed to warm to room temperature and stirred for 2 h. The final dark suspension (almost black) was concentrated under vacuum and the residue was extracted with 50 mL of toluene. The extract was dried under vacuum to give 4.06 g of a brown product, which was characterized by ¹H-NM spectroscopy. The ¹H-NM analysis showed the presence of the desired ligand (78.5 wt %) together with 15.1 wt % of starting IndSiMe₂Cl and 6.4 wt % of toluene. The ligand was used as such in the next step without further purification.

Yield of the pure product=79.9%. ¹H NMR (δ, ppm, CDCl₃): −0.39 (s, 3H, Si—CH₃); −0.20 (s, 3H, Si—CH₃); 2.57 (s, 6H, CH₃); 3.82 (t, 1H, CH, J=1.85 Hz); 3.89 (s, 1H, CH); 6.45 (dd, 1H, CH, J=5.33 Hz, J=1.85 Hz); 6.77–7.52 (m, 7H, Ar).

Synthesis of dimethylsilyl{(1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-10

A 2.5 M solution of n-BuLi in hexane (9.00 mL, 22.50 mmol) was added at −20° C. to a solution of 4.06 g of (1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane (Mw=378.64, 10.72 mmol, n-BuLi:ligand=2:1 considering the ligand 100% pure) in 50 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. with final formation of a dark brown suspension. This suspension was cooled again at −20° C. and added of a suspension of 2.50 g of ZrCl₄ (Mw=233.03, 10.72 mmol, ZrCl₄:ligand=1:1 considering the ligand 100% pure) in 50 mL of pentane, previously cooled to −20° C. The reaction mixture was kept at −20° C. for 20 min, then allowed to warm to room temperature and stirred for 2 h. The final orange-brown suspension was evaporated off under vacuum and the residue extracted with 50 mL of toluene. The extract was eliminated, while the insoluble in toluene was washed with ether to give an orange powder (4.10 g), which resulted to be the desired catalyst by ¹H-NMR An aliquot of this powder (1.50 g) was washed very quickly with EtOH (10 mL) and subsequently with Et₂O. After drying 0.90 g of pure catalyst as orange powder was recovered. Yield of the crude product (with LiCl)=71.0%.

¹H NMR (δ, ppm, CD₂Cl₂): 1.01 (s, 3H, Si—CH₃); 1.29 (s, 3H, Si—CH₃); 2.46 (d, 3H, CH₃, J=1.17 Hz); 2.58 (d, 3H, CH₃, J=1.17 Hz); 6.07 (d, 1H, CH, J=3.28 Hz); 6.70 (q, 1H, CH, J=1.17 Hz); 6.85 (q, 1H, CH, J=1.17 Hz); 6.90–7.64 (m, 5H, Ar).

Example 11 Synthesis of chloro(2-methyl-1-indenyl)dimethylsilane

A 2.5 M n-BuLi solution in hexane (22.1 mL, 55.25 mmol, n-BuLi:2-Me-indene=1.1:1) was added dropwise to a solution of 6.54 g of 2-methylindene (Boulder Scientific Company 419-0128, MW=130.19, 50.23 mmol) in 70 mL of Et₂O, previously cooled to −20° C. At the end of the addition, the mixture was kept at −20° C. for 15 min, then allowed to warm to room temperature and stirred overnight. The solvents were evaporated off under reduced pressure to give a pale orange solid, which was taken up in 50 mL of hexane; the suspension was stirred for 10 minutes at room temperature and filtered. The lithium salt of 2-methylindene on the filter was washed with hexane (2×10 mL) and dried. The solid was again slurried in 70 mL of hexane and added to a stirred solution of Me₂SiCl₂ (9.1 mL, d=1.064, MW=129.06, 75.02 mmol, Me₂SiCl₂/2-Me-IndLi=1.5:1) in 60 mL of hexane, previously cooled to □20° C. At the end of the addition, the pale orange slurry was kept at −20° C. for 15 min, then allowed to warm to room temperature and stirred overnight. The final white-pale yellow suspension was filtered and the filtrate brought to dryness in vacuo at 40° C. to yield a yellow-orange oil as product (8.40 g). Yield=75.1%. Purity=89.1%.

¹H NMR (δ, ppm, CDCl₃): 0.22 (s, 3H, Si—CH₃), 0.47 (s, 3H, Si—CH₃), 2.36 (m, 3H, CH₃), 3.65 (bs, 1H, CH), 6.70 (m, 1H, Cp-H), 7.18–7.56 (m, 4H, Ar). About 6% (by GC-MS) of bis(2-methyl-1-indenyl)dimethylsilane (rac/meso=1.3:1) was also present. m/z (%): 224 (28) [M⁺+2], 222 (74) [M⁺], 129 (20), 128 (67), 127 (17), 95 (35), 93 (100).

Alternative Process Without 2-Me-1-IndLi⁺ Salt Isolation

A 2.5 M n-BuLi solution in hexane (23.6 mL, 59.00 mmol, n-BuLi:2-Me-indene=1:1) was added dropwise to a solution of 7.87 g of 2-methylindene (B3Boulder Scientific Company 419-0128, MW=130.19, 97.6%, 59.00 mmol) in 50 mL of Et₂O, previously cooled to 0° C. At the end of the addition, the mixture was kept at 0° C. for 15 min, then allowed to warm to room temperature and stirred for 2 h with final formation of a pale yellow suspension. It was cooled again to 0° C. and added dropwise of Me₂SiCl₂ (7.86 mL, d=1.064, MW=129.06, 64.80 mmol, Me₂SiCl₂/2-Me-IndLi=1.1:1). At the end of the addition, the reaction mixture was allowed to warm to room temperature and stirred overnight. The final white-pale yellow suspension was concentrated in vacuo and the residue extracted with 30 mL of toluene. The extract was brought to dryness in vacuo at 40° C. to yield a orange oil as product (10.41 g).

Yield=79.2%. Purity=83.6%. Traces of starting 2-methylindene and 9.8% of bis(2-methyl-1-indenyl)dimethylsilane (by GC-MS) were also present. m/z for bis(2-methyl-1-indenyl)dimethylsilane (%): 316 (21) [M⁺], 187 (100), 159 (24), 128 (18), 59 (57).

Synthesis of (2-methyl-I-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene) dimethylsilane

A 2.5 M solution of n-BuLi in hexane (4.15 mL, 10.37 mmol) was added at −20° C. to a solution of 2.13 g of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene (Mw 206.32, 87.9% by GC-MS, 9.07 mmol, n-BuLi: MeTh₂Cp=1.1:1) in 20 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. with final formation of a dark brown solution. This solution was cooled again to −20° C. and added of a solution of 2.03 g of chloro(2-methyl-1-indenyl)dimethylsilane 9.10 mmol, (2-Me-1-Ind)SiMe₂Cl:MeTh₂Cp=1:1) in 3 mL of ether. The reaction mixture was then allowed to warm to room temperature and stirred for 2 h. The final dark solution (almost black) was concentrated under vacuum and the sticky residue was extracted with 50 mL of toluene. The extract was dried under vacuum to give 3.93 g of a brown sticky product, which was characterized by GC-MS analysis and ¹H-NMR spectroscopy. The ¹H-NMR analysis showed the presence of the desired ligand together with 10 wt % of toluene.

Purity (by GC-MS)=90.4%. Yield of the pure product=89.9%. ¹H NMR (δ, ppm, CDCl₃): −0.37 (s, 6H, Si—CH₃); 2.26 (d, 3H, CH₃, J=0.8 Hz); 2.56 (dd, 3H, CH₃, J=1.1 Hz, J=0.6 Hz ); 2.58 (dd, 3H, CH_(3,) J=1.1 Hz, J=0.6 Hz); 3.88 (bs, 1H, CH); 4.04 (s, 1H, CH); 6.65–6.66 (m, 1H, CH); 6.87 (q, 1H, CH, J=1.1 Hz); 6.89 (q, 1H, CH, J=1.1 Hz); 7.10–7.50 (m, 4H, Ar). m/z (%): 393 (13) [M⁺+1], 392 (40) [M⁺], 263 (100), 235 (18), 187 (44), 159 (15), 59 (13).

Synthesis of dimethylsilyl{(2-methyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-20

A 2.5 M solution of n-BuLi in hexane (7.20 mL, 18.00 mmol) was added at −20° C. to a solution of 3.93 g of (2-methyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane (Mw=392.66, 90.4% by GC-MS, 8.15 mmol, n-BuLi:ligand=2:1 considering the ligand 90.4% pure) in 30 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. and 30 min at room temperature with final formation of a dark brown suspension. This suspension was cooled again at −20° C. and added of a suspension of 1.91 g of ZrCl₄ (Mw=233.03, 8.20 mmol, ZrCl₄:ligand=1:1 considering the ligand 90.4% pure) in 50 mL of pentane, previously cooled to −20° C. The reaction mixture was kept at −20° C. for 1 h, then allowed to warm to room temperature and stirred overnight. The final orange-pale brown suspension was evaporated off under vacuum and the residue washed with ether to give an orange powder (5.32 g), which was analysed by ¹H-NMR in CD₂Cl₂. The ¹H-NMR analysis showed the presence of the desired catalyst together with an adduct of coordination not identified probably ZrCl₄(Et₂O)₂ or LiCl(Et₂O)). The powder was washed very quickly with 15 mL of HCl 4N, then with water (30 mL), subsequently with EtOH (20 mL) and finally with Et₂O. After drying 3.50 g of pure catalyst as orange powder was recovered. Yield of the pure product=77.7%.

¹H NMR (δ, ppm, CD₂Cl₂): 1.20 (s, 3H, Si—CH₃); 1.35 (s, 3H, Si—CH₃); 2.39 (d, 3H, CH₃J=0.59); 2.45 (d, 3H, CH₃, J=1.2 Hz); 2.62 (d, 3H, CH₃, J=1.2 Hz); 6.66 (q, 1H, CH, J=1.2 Hz); 6.81 (bs, 1H, CH); 6.87 (ddd, 1H, CH, J=0.98 Hz, J=6.65 Hz, J=9.0 Hz); 7.21 (ddd, 1H, CH, J=0.98 Hz, J=6.65 Hz, J=8.61 Hz); 7.45 (dt, 1H, CH, J=0.98, Hz J=8.61 Hz); 7.73 (dq, 1H, CH, J=0.98 Hz, J=9.0 Hz).

Example 12 Synthesis of chloro(2-methyl-4-phenyl-1-indenyl)dimethylsilane

A 2.5 M solution of n-BuLi in hexane (4.85 mL, 12.12 mmol) was added at 0° C. to a solution of 2.50 g of 2-methyl-4-phenyl-indene (Boulder Scientific Company, Mw=206.29, 12.12 mmol, n-BuLi:2-Me-4-Ph-Ind=1:1) in 30 mL of ether. The resulting mixture was stirred for additional 2 h at room temperature with final formation of an orange solution. This solution was cooled again to 0° C. and added slowly of a solution of 1.58 mL of dichlorodimethylsilane (Aldrich, Mw=129.06, d=1.064, 13.03 mmol, Me₂SiCl₂:2-Me-4-Ph-Ind=1.08:1) in 20 mL of ether. The reaction mixture was then allowed to warm to room temperature and stirred for 1 h. The final straw yellow suspension was concentrated under vacuum and the residue was extracted with 50 mL of toluene. The extract was dried under vacuum to give 3.36 g of a straw yellow solid, which was characterized by GC-MS analysis and ¹H-NMR spectroscopy. Yield=92.8%.

¹H NMR (δ, ppm, CDCl₃): 0.24 (s, 3H, Si—CH₃); 0.48 (s, 3H, Si—CH₃); 2.31 (d, 3H, CH₃J=0.78 Hz); 3.70 (bs, 1H, CH); 6.85 (m, 1H, CH, J=0.78 Hz); 7.19–7.59 (m, 8H, Ar). m/z (%): 300 (26) [M⁺+2], 299 (18) [M⁺+1], 298 (72) [M⁺]; 205 (23), 204 (45), 203 (28), 202 (32), 189 (15), 165 (13), 95 (35), 93 (100).

Synthesis of (2-methyl-4-phenyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A 2.5 M solution of n-BuLi in hexane (2.72 mL, 6.80 mmol) was added at −20° C. to a solution of 1.40 g of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene (Mw=206.32, 90.7%, 6.15 mmol, n-BuLi:MeTh₂Cp=1.1:1) in 30 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. with final formation of a dark brown suspension. This suspension was cooled again to −20° C. and added slowly of a solution of 1.90 g of chloro(2-methyl-4-phenyl-1-indenyl)dimethylsilane (Mw=298.89, 6.37 mmol, (2-Me-4-Ph-1-Ind)SiMe₂Cl:MeTh₂Cp=1.04:1) in 20 mL of ether. The reaction mixture was then allowed to warm to room temperature and stirred for 2 h. The final dark solution (almost black) was concentrated under vacuum and the residue extracted with 50 mL of toluene to give an oily product, which was treated at 30° C. under stirring with 30 mL of pentane. After 15 min stirring a powdery solid was formed and isolated by filtration. After drying in vacuo, 2.03 g of a brown product was recovered.

Purity (by GC-MS)=83.8%. Yield of the pure product=59.0%. ¹H NMR (δ, ppm, CDCl₃): −0.35 (s, 3H, Si—CH₃); −0.32 (s, 3H, Si—CH₃); 2.23 (d, 3H, CH₃, J=0.78 Hz); 2.55 (bs, 3H, CH₃); 2.58 (bs, 3H, CH₃); 3.96 (s, 1H, CH); 4.04 (s, 1H, CH); 6.82 (q, 1H, CH, J=0.78 Hz); 6.86 (q, 1H, CH, J=1.17 Hz); 6.88 (q, 1H, CH, J=1.17 Hz); 7.13–7.59 (m, 8H, Ar). m/z (%): 469 (10) [M⁺+1], 468 (24) [M⁺], 264 (28), 263 (100), 248 (14), 247 (21), 235 (20), 205 (13), 203 (16), 190 (10), 59 (14).

Synthesis of dimethylsilyl{(2-methyl-4-phenyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-28

A solution of 2.58 g (5.5 mmol) of (2-methyl-4-phenyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane in 40 mL of ether was treated at −70° C. with 7.0 mL of a 1.6 M n-BuLi solution (11.2 mmol). The reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.28 g (5.5 mmol) of ZrCl were added. The reaction mixture was stirred at room temperature overnight, the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.65 g (48%). The title compound was characterized by ¹H NMR spectroscopy.

Example 13 Synthesis of (2-methyl-1-indenyl)-7-(cyclopenta[1,2-b:4,3-b′]-dithiophene) dimethylsilane

A 2.5 M solution of n-BuLi in hexane (1.50 mL, 3.75 mmol) was added at −20° C. to a solution of 1.29 g of 711-cyclopenta[1,2-b:4,3-b′]-dithiophene (Mw=178.28, purity valued by ¹H NMR ca. 50 wt %, 3.62 mmol, n-BuLi:TH₂Cp=1.04:1) in 20 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. with final formation of a dark brown suspension. This suspension was cooled again to −20° C. and added of a solution of 0.96 g of chloro(2-methyl-1-indenyl)dimethylsilane (83,6% by GC-MS, Mw=222.79, 3.62 mmol, (2-Me-1-Ind)SiMe₂Cl:Th₂Cp=1:1) in 5 mL of ether. The reaction mixture was then allowed to warm to room temperature and stirred for 2 h. The final black suspension was concentrated under vacuum and the stick residue was extracted with 30 mL of toluene to remove the LiCl formed. The extract was dried under vacuum to give 2.26 g of a black oil, which was analysed by ¹H-NMR spectroscopy. Starting chloro(2-methyl-1-indenyl)dimethylsilane, hexaethylsiloxane coming from previous steps and tars were also present as by-products, but attempts to purify the desired ligand failed because of the high solubility of the mixture in apolar solvent as pentane. The crude product was then used as such in the next step without further purification.

¹H NMR (δ, ppm, CDCl₃): −0.36 (s, 3H, Si—CH₃); −0.35 (s, 3H, Si—Cl₃); 2.26 (d, 3H, CH₃, J=0.98 Hz); 3.89 (s, 1H, CH); 4.15 (s, 1H, CH); 6.69–7.52 (m, 9H, Ar).

Synthesis of dimethylsilyl{(2-methyl-1-indenyl)-7-(cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-36

A 2.5 M solution of n-BuLi in hexane (5.00 mL, 12.50 mmol) was added at −20° C. to a solution of 2.26 g of (2-methyl-1-indenyl)-7-(cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane (Mw=364.61, 6.20 mmol, n-BuLi:ligand=2.02:1 considering the ligand 100% pure) in 20 mL of ether. The resulting mixture was stirred for additional 1 h at 0° C. with final formation of a brown suspension. This suspension was cooled again to −20° C. and added of a suspension of 1.44 g of ZrCl₄ (Mw=233.03, 6.20 mmol, ZrCL₄:ligand=1:1 considering the ligand 100% pure) in 30 mL of pentane, previously cooled to −20° C. The reaction mixture was kept at −20° C. for 1 h, then allowed to warm up slowly to room temperature and stirred for 3 h. The final brown suspension was evaporated off under vacuum and the residue extracted with 30 mL of toluene: the extract, containing mainly tars, was eliminated, while the brown residue (3.33 g) was dried and washed with 20 mL of ether. The ¹H-NMR analysis in CD₂Cl₂ showed for the residue from ether the presence of the desired catalyst together with an adduct of coordination not identified probably ZrCl₄(Et₂O)₂ or LiCl(Et₂O)) and few tars. Again the brown powder (2.28 g) was washed very quickly with 20 mL of CH₂Cl₂, then with EtOH (10 mL) and finally with Et₂O (15 mL). After drying 0.44 g of catalyst as pale brown powder was recovered. Yield=13.5%.

¹H NMR (δ, ppm, CD₂Cl₂): 1.25 (s, 3H, Si—CH₃); 1.41 (s, 3H, Si—CH₃); 2.38 (bs, 3H, CH₃); 6.82–7.79 (m, 9H, Ar).

Example 14 Synthesis of chlorodimethyl-(2-phenyl-1-indenyl)silane

A solution of 0.96 g (5.0 mmol) of 2-phenylindene in 30 mL of Et₂O was treated at −70° C. with 3.13 mL (5.0 mmol) of a 1.6 M solution of n-BuLi. After the addition, the mixture was allowed to warm to room temperature and stirred for 50 min. Then it was cooled again to −70° C. and treated with a solution of 0.65 g (5.0 mmol) of Me₂SiCl₂ in 10 mL of ether. When the addition was completed, the mixture was allowed to reach room temperature and stirred overnight. The resulting reaction mixture was filtered to remove LiCl and the solvent was removed under reduced pressure. The crude product was used in the next step without further purification.

¹H-NMR (δ, ppm, C₆D₆): 7.90–7.10 (m, 9H, CH); 6.95 (s, 1H, CH); 4.15 (s, 1H, CH); −0.02 (s, 3H, Si—CH₃); −0.20 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{(2-phenyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-31

A suspension of 1.03 g (5.0 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 30 mL of ether was treated at −70° C. with 3.13 mL of a 1.6 M n-BuLi solution (5.0 mmol). After the addition, the resulting mixture was allowed to warm to room temperature and stirred for additional 50 min at this temperature. Then it was cooled again to −70° C. and added of an etheral solution (10 mL) of chlorodimethyl-(2-phenyl-1-indenyl)silane coming from the previous step. The mixture was allowed to warm to room temperature and stirred overnight. The ligand (2-phenyl-1-indenyl)-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}dimethylsilane was characterized by ¹H-NMR spectroscopy.

¹H-NMR (δ, ppm, CDCl₃): 7.70–7.25 (m, 9H, CH); 7.20 (s, 1H, CH); 6.90 (m, 2H, CH); 4.60 (s, 1H, CH); 3.70 (s, 1H, CH); 2.65 (s, 3H, CH₃); 2.60 (s, 3H, CH₃); −0.44 (s, 3H, Si—CH₃); −0.66 (s, 3H, Si—CH₃).

The ligand was not isolated: its solution was treated at −70° C. with 7.0 mL of a 1.6 M n-BuLi solution (11.2 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.28 g (5.5 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the red precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂.

Yield 1.64 g (53% based on Me₂Th).

Example 15 Synthesis of (2-methyl-1-indenyl)-7-(2,5-diethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A suspension of 1.17 g (5.0 mmol) of 2,5-diethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 75 mL of ether was treated at −70° C. with 3.13 mL of a 1.6 M n-BuLi solution (5.0 mmol). After the addition, the mixture was allowed to warm to room temperature and stirred for additional 1 h at this temperature. Then it was cooled again to −70° C. and added of a solution of 1.11 g (5 mmol) of chloro(2-methyl-1-indenyl)dimethylsilane in 10 mL of ether. The resulting mixture was allowed to reach room temperature and stirred overnight. The ligand (2-methyl-1-indenyl)-7-(2,5-diethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane was not isolated, but used in solution for the catalysts synthesis (see below).

¹H-NMR (δ, ppm, CDCl₃): 7.55 (d, 1H, CH); 7.44 (d, 1H, CH); 7.28 (m, 1H, CH); 7.15 (m, 1H, CH); 6.98 (m, 1H, CH); 6.96 (m, 1H, CH); 6.70 (m, 1H, CH); 4.10 (s, 1H, CH); 3.94 (s, 1H, CH); 2.98 (m, 4H, CH₂); 2.31 (s, 3H, CH₃); 1.43 (t, 3H, CH₃); 1.41 (t, 3H, CH₃); −0.30 (s, 3H, Si—CH₃); −0.31 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{(2-methyl-1-indenyl)-7-(2,5-diethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-34

The ligand solution coming from the previous step was treated at −70° C. with 7.0 mL of a 1.6 M n-BuLi solution (11.2 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt so-obtained was suspended in hexane. After cooling to −70° C., 0.75 g (3.2 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the yellowish-red precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.52 g (52% with respect to Et₂Th).

Example 16 Synthesis of (2-methyl-1-indenyl)-7-(2,5-diphenyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A solution of 1.32 g (4.0 mmol) of 2,5-diphenyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 30 mL of ether was treated at −70° C. with 2.50 mL of a 1.6 M n-BuLi solution (4.0 mmol). After the addition, the mixture was allowed to warm to room temperature and stirred for additional 50 min at this temperature. Then it was cooled again to −70° C. and added of a solution of 0.90 g (4.0 mmol) of chlorodimethyl(2-methyl-1-indenyl)silane in 10 mL of ether. The resulting mixture was allowed to reach room temperature and stirred overnight. The ligand (2-methyl-1-indenyl)-7-(2,5-diphenyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane was not isolated, but used in solution for the catalysts synthesis.

Synthesis of dimethylsilyl{(2-methyl-1-indenyl)-7-(2,5-diphenyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-35

The ligand solution coming from the previous step was treated at −70° C. with 5.6 mL of a 1.6 M n-BuLi solution (9.0 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for additional 1 h After cooling to −70° C., 1.05 g (4.5 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, then the violet precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂.

Yield 1.27 g (47% with respect to Ph₂Th).

Example 17 Synthesis of 3,6,6-trimethylfulvene

A solution of 2-methyl-1,3-cyclopentadiene (125 g, 1.56 mol) in 1.2 L of ethanol was treated at low temperature with 126 mL (1.72 mol) of acetone and 142 mL (1.72 mol) of pyrrolidine. The resulting solution was kept below room temperature overnight. Then the reaction mixture was neutralized with a 10% aq. solution of H₃PO₄, extracted with hexane (3×150 mL) and washed with water until neutral pH. The organic phase was separated, dried with MgSO₄ and concentrated. The residue was distilled at 70° C./60 mmHg. Yield 112.6 g (60%).

¹H NMR (δ, ppm, CDCl₃): 6.53 (dd, 1H, CH); 6.35 (dd, 1H, CH); 6.20 (m, 1H, CH); 2.17 (s, 3H, CH₃); 2.16 (s, 3H, CH₃); 2.09 (s, 3H, CH₃).

Synthesis of 3-isopropyl-1-methyl-1,3-cyclopentadiene

A solution of 24 g (0.2 mol) of 3,6,6-trimethylfulvene in 100 mL of ether was added at 78° C. under argon atmosphere to a solution of 7.59 g (0.2 mol) of lithium aluminium hydride in 200 mL of ether. The reaction mixture was allowed to warm to room temperature, stirred for 2 h and then treated with a 10% aq. solution of NH₄Cl. The organic phase was collected, washed with water, dried with MgSO₄ and concentrated. The residue was distilled at 63° C./50 mmHg. Yield 15.88 g (65%).The desired title compound was characterized by ¹H-NR

Synthesis of 1-methyl-3-isopropyl-6,6-dimethylfulvene

3-isopropyl-1methyl-1,3-cyclopentadiene (39 g, 0.32 mol) was added at low temperature to a suspension of 12.8 g (0.32 mol) of sodium hydroxide in 200 mL of dry THF. After 30 min stirring, the reaction mixture was treated with 23.8 mL (0.32 mol) of acetone. The resulting solution was kept below room temperature overnight. Then the resulting mixture was neutralized with a 10% aq. solution of H₃PO₄, extracted with hexane (3×100 mL) and washed with water until neutral pH. The organic phase was separated, dried with MgSO₄ and concentrated. The residue was distilled at 80° C./10 mmHg. Yield 25.96 g (50%).

¹H NMR (δ, ppm, CDCl₃): 6.21 (m, 1H, CH); 6.05 (d, 1H, CH); 2.67 (m, 1H, CH); 2.24 (s, 3H, CH₃); 2.21 (s, 3H, CH₃); 2.20 (s, 3H, CH₃); 1.26 (s, 3H, CH₃); 1.28 (s, 3H, CH₃).

Synthesis of 2,2-(2-methyl-4-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]dithiophene)propane

A 1.6 M solution of n-BuLi (6.25 mL, 10 mmol) was added at −70° C. to a suspension of 2.06 g (10 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 100 mL of ether. At the end of the addition, the mixture was allowed to warm to room temperature and stirred for additional 50 min at the same temperature. The resulting reaction mixture was treated at −70° C. with a solution of 0.74 g (5 mmol) of 1-methyl-3-isopropyl-6,6-dimethylfulvene, then was allowed to warm to room temperature and stirred overnight. The final mixture was poured into 100 mL of a 10% aq. solution of NH₄Cl and extracted with hexane (2×50 mL). The organic phase was collected, washed with water, dried with MgSO₄ and evaporated off. The residue was passed through a column packed with SiO₂ by using hexane as eluent. The resulting solution was dried giving the crystalline product. Yield 1.5 g (41% based on starting MeTh₂Cp).

Synthesis of isopropilydene{(2-methyl-4-isopropyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-17

A suspension of 1.11 g (3 mmol) of 2,2-(2-methyl-4-isopropyl-1-cyclopentadienyl)-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]dithiophene)}propane in 10 mL of ether and 50 mL of hexane was treated at −70° C. with 3.8 mL of a 1.6 M n-BuLi solution (6.1 mmol). After the addition, the reaction mixture was allowed to warm to 0° C. and added of 0.75 g (3.2 mmol) of ZrCl₄. The resulting mixture was allowed to reach room temperature and stirred overnight. Then the yellow precipitate obtained was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂.

Yield 1.43 g (90%). ¹H-NMR (δ, ppm, CD₂Cl₂): 6.88 (m, 1H, CH); 6.80 (m, 1H, CH); 6.10 (d, 1H, CH); 5.58 (d, 1H, CH); 2.78 (m, 1H, CH); 2.58 (m, 3H, CH₃); 2.56 (d, 3H, CH₃); 2.40 (s, 3H, CH₃); 2.18 (s, 3H, CH₃); 1.96 (s, 3H, CH₃); 1.14 (d, 3H, CH₃); 1.08 (d, 3H, CH₃).

Example 18 Synthesis of 1,3-dimethyl-1,3-cyclopentadiene

A solution of 25 g (0.26 mol) of 3-methyl-2-cyclopenten-1-one in 100 mL of ether was added at −78° C. under argon atmosphere to a solution of methyl litium in 200 mL of ether, previous prepared from 5.76 g (0.83 mol) of lithium and 26 mL (0.42 mol) of iodomethane. The reaction mixture was stirred for 4 h and then treated with a 10% aq. solution of NH₄Cl. The organic phase was collected, washed with water, dried with MgSO₄ and concentrated. The residue was distilled at 42° C./100 mmHg. Yield 7.3 g (30%).

¹H-NMR (δ, ppm, CD₃COCD₃): 5.98 (m, 1H, CH); 5.75 (m, 1H, CH); 2.80 (m, 2H, CH₂); 2.02 (d, 3H, CH₃); 1.90 (d, 3H, CH₃).

The ligand synthesis was carried out by coupling the lithium salt of the MeTh₂Cp precursor with chloro(2,4-dimethylcyclopentadienyl)dimethylsilane, previous prepared from the lithium salt of 1,3-dimethyl-1,3-cyclopentadiene and Me₂SiCl₂.

Synthesis of dimethylsilyl{(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-18

A suspension of 1.07 g (3 mmol) of (2,4-dimethyl-cyclopentadienyl)-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]dithiophene)}dimethylsilane in 20 mL of ether was treated at −70° C. with 4.1 mL of a 1.6 M n-BuLi solution (6.5 mmol). After the addition, the reaction mixture was allowed to warm to 0° C. and added of 0.75 g (3.2 mmol) of ZrCl₄. The resulting mixture was allowed to reach room temperature and stirred overnight. Then the yellow precipitate obtained was filtered, washed twice with ether, dried and finally recrystallyzed from CH₂Cl₂.

Yield 1.35 g (87%). ¹H-NMR (δ, ppm, CD₂Cl₂): 6.93 (m, 1H, CH); 6.87 (m, 1H, CH); 6.80–6.70 (m, 1H, CH); 6.25 (t, 1H, CH); 2.59 (d, 3H, CH₃); 2.56 (d, 3H, CH₃); 2.18 (s, 3H, CH₃); 2.11 (s, 3H, CH₃); 1.03 (s, 3H, Si—CH₃); 0.84 (s, 3H, Si—CH₃).

Example 19 Synthesis of dimethylsilyl{(3-tert-butyl-cyclopentadienyl-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C4

The synthesis was carried out by following the same procedure described in the Example 18 by using 3-tert-butyl-1,3-cyclopentadiene instead of 1,3-dimethyl-1,3cyclopentadiene. The product was characterized by NMR spectroscopy.

Example 20 Synthesis of isopropilydene{(tetramethyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-5

The synthesis was carried out by following the same procedure described in the Example 17 by using 1,2,3,4,6,6-esamethylfulvene instead of 1-methyl-3-isopropyl-6,6-dimethylfulvene. The product was characterized by NMR spectroscopy.

Example 21 Synthesis of dimethylsilyl{(3-trimethylsilyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}

The ligand synthesis was carried out by coupling the lithium salt of the MeTh₂Cp precursor with chloro(3-trimethylsilyl-cyclopentadienyl)dimethylsilane, previous prepared from the lithium salt of trimethylsilyl-1,3-cyclopentadiene and Me₂SiCl₂.

Synthesis of dimethylsilyl{(3-trimethylsilyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-9

A suspension of 1.20 g (3 mmol) of (3-trimethylsilyl-1-cyclopentadienyl)-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]dithiophene)}dimethylsilane in 20 mL of ether was treated at −70° C. with 4.1 mL of a 1.6 M n-BuLi solution (6.5 mmol). After the addition, the reaction mixture was allowed to warm to 0° C. and added of 0.75 g (3.2 mmol) of ZrCl₄. The resulting mixture was allowed to reach room temperature and stirred overnight Then the yellow precipitate obtained was filtered, washed twice with ether, dried and finally recrystallyzed from CH₂Cl₂.

Yield 1.17 g (70%). ¹H-NMR (δ, ppm, CD₂Cl₂): 6.91 (m, 1H, CH); 6.88 (m, 1H, CH); 6.78 (m, 1H, CH); 6.08 (t, 1H, CH); 5.83 (t, 1H, CH); 2.59 (d, 3H, CH₃); 2.57 (d, 3H, CH₃); 0.91 (s, 3H, Si—CH₃); 0.89 (s, 3H, Si—CH₃); 0.20 (s, 9H, Si(CH₃)₃).

Example 22 Synthesis of 1-methyl-3-phenyl-1,3-cyclopentadiene

A solution of 25 g (0.26 mol) of 3-methyl-2cyclopenten-1-one in 100 mL of ether was added at −78° C. under argon atmosphere to a solution of phenyl litium in 200 mL of ether, previous prepared from 5.76 g (0.83 mol) of lithium and 44 mL (0.42 mol) of bromobenzene. The reaction mixture was stirred for 4 h and then treated with a 10% aq. solution of NH₄Cl. The organic phase was collected, washed with water, dried with MgSO₄ and concentrated. The residue was distilled at 54° C./1 mmHg. Yield 24.37 g (60%).

¹H-NMR (δ, ppm, CD₃COCD₃): 7.60–7.10 (m, 5H, CH); 6.80 (d, 1H, CH); 6.00 (m, 1H, CH); 3.00 (s, 2H, CH₂); 1.98 (q, 3H, CH₃).

Synthesis of 1-methyl-3-phenyl-6,6-dimethylfulvene

A solution of 1-methyl-3-phenyl-1,3-cyclopentadiene (15.62 g, 0.1 mol) in 100 mL of ethanol was treated at low temperature with 8.6 mL (0.12 mol) of acetone and 9.7 mL (0.12 mol) of pyrrolidine. The resulting solution was kept below room temperature overnight. Then the reaction mixture was neutralized with a 10% aq. solution of H₃PO₄, extracted with hexane (3×50 mL) and washed with water until neutral pH. The organic phase was separated, dried with MgSO₄ and concentrated. The residue was distilled at 85° C./10 mmHg. Yield 5.89 g (30%). The desired title compound was characterized by ¹H-NMR.

The ligand synthesis was carried out by following the same procedure described in the Example 17, by using 1-methyl-3-phenyl-6,6-dimethylfulvene instead of 1-methyl-3-isopropyl-6,6-dimethylfulvene and 2,5-ditrimethylsilyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene instead of MeTh₂Cp.

Synthesis of isopropilydene{(2methyl-4-phenyl-cyclopentadienyl)7-(2,5-trimethylsilylcyclopenta [1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-14

A suspension of 2.0 g (3.85 mmol) of 2,2-(2-methyl-4-phenyl-1-cyclopentadienyl)-7-(2,5-trimethylsilylcyclopenta[1,2-b:4,3-b′]-dithiophene)propane in 50 mL of ether was treated at −70° C. with 4.8 mL of a 1.6 M n-BuLi solution (7.71 mmol). After the addition, the reaction mixture was allowed to warm to 0° C. and added of 0.90 g (3.85 mmol) of ZrCl₄. The resulting mixture was allowed to reach room temperature and stirred overnight. Then the brown precipitate obtained was filtered, washed twice with ether, dried and finally recrystallyzed from CH₂Cl₂. Yield 1.82 g (70%).

¹H-NMR (δ, ppm, CD₂Cl₂): 7.34 (s, 2H, CH); 7.32–7.12 (m, 5H, CH); 6.62 (d, 1H, CH); 6.26 (d, 1H, CH); 2.50 (s, 3H, CH₃); 2.30 (s, 3H, CH₃); 2.10 (s, 3H, CH₃); 0.36 (s, 9H, Si(CH₃)₃; 0.32 (s, 9H, Si(CH₃)₃).

Example 23 Synthesis of isopropilydene{(2-methyl-4-phenyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-11

The synthesis was carried out by following the same procedure described in the Example 22 by using 2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene instead of 2,5-trimethylsilylcyclopenta [1,2-b:4,3-b′]-dithiophene. The product was characterized by NMR spectroscopy.

Example 24 Synthesis of isopropilydene{(4-phenyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-19

The synthesis was carried out by following the same procedure described in the Example 22 by using 3-phenyl-6,6-dimethylfulvene instead of 1-methyl-3-phenyl-6,6-dimethylfulvene. The product was characterized by NMR spectroscopy.

Example 25 The synthesis of 1,3-dimethyl-1,3-cyclopentadiene has been reported above in the Example 18. Synthesis of 1,3,6,6-tetramethylfulvene

A solution of 1,3-dimethyl-1,3-cyclopentadiene (9.42 g, 0.1 mol) in 100 mL of ethanol was treated at low temperature with 8.6 mL (0.12 mol) of acetone and 9.7 mL (0.12 mol) of pyrrolidine. The resulting solution was kept below room temperature overnight. Then the reaction mixture was neutralized with a 10% aq. solution of H₃PO₄, extracted with hexane (3×50 mL) and washed with water until neutral pH. The organic phase was separated, dried over MgSO₄ and concentrated. The residue was distilled at 63° C./20 mmHg. Yield 6.7 g (50%).

¹H NMR (δ, ppm, CDCl₃): 6.08 (m, 1H, CH); 6.03 (m, 1H, CH); 2.23 (d, 3H, CH₃); 2.17 (s, 3H, CH₃); 2.16 (s, 3H, CH₃); 1.99 (s, 3H, CH₃).

The ligand synthesis was carried out by following the same procedure described in the Example 17, by using 1,3,6,6-tetramethylfulvene instead of 1-methyl-3-isopropyl-6,6-dimethylfulvene and 2,5-ditrimethylsilyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene instead of MeTh₂Cp.

Synthesis of isopropilydene{(2,4-dimethyl-cyclopentadienyl)-7-(2,5-trimethylsilylcyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-15

A suspension of 2.19 g (4.8 mmol) of 2,2-(2,4-dimethyl-1-cyclopentadienyl)-7-(2,5-trimethylsilylcyclopenta[1,2-b:4,3-b′]-dithiophene)propane in 50 mL of ether was treated at −70° C. with 6.0 mL of a 1.6 M n-BuLi solution (9.6 mmol). After the addition, the reaction mixture was allowed to warm to 0° C. and added of 1.12 g (4.8 mmol) of ZrCl₄. The resulting mixture was allowed to reach room temperature and stirred overnight. Then the red-brown precipitate obtained was filtered, washed twice with ether, dried and finally recrystallyzed from CH₂Cl₂. Yield 2.07 g (70%). The desired title compound was characterized by ¹H-NMR.

Example 26 Synthesis of 3-chloro-2-methyl-2-butenal

1.3 mol (120 mL) of POCl₃ was added at 0° C. to a 1.6 mol (120 mL) of DMF. At the end of the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to 0° C. and treated with 1 mol (90 mL) of 2-butanone. The resulting reaction mixture was allowed to reach room temperature and stirred overnight. Then it was poured into a mixture of ice and water, added of sodium acetate and extracted with CHCl₃ (3×150 mL). The organic phase was separated, washed with water until neutral pH, dried over MgSO₄ and evaporated off to dryness. The residue was distilled in vacuo, b.p. 45° C./10 torr. Yield 73 g (62%).

Synthesis of 4,5-dimethyl-2-thiophene-ethylcarboxylate

Ethyl-2-mercaptoacetate (0.2 mol, 24 g) was added at 0° C. to a solution of sodium ethoxide (0.21 mol, 14.3 g) in 150 mL of ethanol and the resulting mixture was stirred at the same temperature for 30 min. Then 3-chloro-2-methyl-2-butenal (0.2 mol, 23.7 g) was added and stirring was continued overnight. The resulting product was diluted in 100 mL of water, the organic layer was collected and the water layer was extracted with CH₂Cl₂ (2×150 mL). The combined organic layers were dried over MgSO₄, evaporated off to dryness and the residue distilled in vacuo. Yield 22.48 g (61%).

¹H-NMR (δ, ppm, CDCl₃): 7.52 (s, 1H, CH); 4.32 (q, 2H, OCH₂); 2.35 (s, 3H, CH₃); 2.12 (s, 3H, CH₃); 1.35 (t, 3H, CH₃).

Synthesis of 4,5-dimethyl-2-thiophenecarboxylic acid

4,5-dimethyl-2-thiophene-ethylcarboxylate (0.122 mol, 22.48 g) was added to a 30% solution of sodium hydroxide in 100 mL of ethanol and the resulting mixture was refluxed for 2 h. Then it was diluted in water, acidified and filtered. The precipitate was dried under P₂O₅.

Yield 15.6 g (82%). ¹H-NMR (δ, ppm, CDCl₃): 7.60 (s, 1H, CH); 2.42 (s, 3H, CH₃); 2.17 (s, 3H, CH₃).

Synthesis of 2,3-dimethylthiophene

The 4,5-dimethyl-2-thiophenecarboxylic acid prepared as described above (0.58 mol, 90 g) was heated to 180° C. until the evolution of carbon dioxide ceased. The product was collected and distilled, b.p. 140° C.

Yield 30 g (46%). ¹H-NMR (δ, ppm, CDCl₃): 7.02 (d, 1H, CH); 6.82 (d, 1H, CH); 2.42 (s, 3H, CH₃); 2.20 (s, 3H, CH₃).

Synthesis of 2,3,5-trimethyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one

A solution of 10 g of P₂O₅ (0.07 mol) in 100 mL of methanesulfonic acid (1.54 mol) was heated at 80° C. under stirring. A mixture of 2,3-dimethylthiophene (0.27 mol, 30 g) and methacrylic acid (0.35 mol) in 20 mL of CH₂Cl₂ was added and the resulting reaction mixture was stirred at the same temperature for 1.5 h. Then it was poured into a mixture of ice and water and stirred vigorously. The water layer was extracted with CH₂Cl₂ (3×50 mL), the organic layers were collected, washed with a 10% aqueous solution of sodium carbonate until neutral pH and finally with water. Then the organic phase was isolated, dried over MgSO₄, evaporated off to dryness and distilled in vacuo, b.p. 110° C./1 torr. Yield 10 g (20%).

¹H-NMR (δ, ppm, CDCl₃): 3.35 (dd, 1H, CH₂); 2.98 (qd, 1H, CH); 2.66 (dd, 1H, CH₂); 2.35 (s, 3H, CH₃); 2.25 (s, 3H, CH₃); 1.52 (d, 3H, CH₃).

Synthesis of 2,3,5-trimethyl-6H-cyclopenta[b]thiophene (or 2,3,5trimethyl-1-thiopentalene)

A solution of 2,3,5-trimethyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one (11 g, 61 mmol) in 100 mL of ether was slowly added to a solution of LiAlH₄ (1.16 g, 30 mmol) in 100 mL of ether and stirred overnight. The resulting suspension was poured into a mixture of ice and water, the organic layer was isolated, while the water layer was extracted with ether (3×50 mL). The combined organic layers were washed with water, dried over MgSO₄ and evaporated off to dryness. The 2,3,5-trimethyl-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ol so obtained was dissolved in 100 mL of benzene, added of 1 g of p-toluenesulfonic acid and was refluxed for 10 min. Then the reaction mixture was cooled to room temperature and treated with a saturated aqueous solution of Na₂CO₃. The organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. Yield 8 g (80% based on starting ketone).

¹H-NMR (δ, ppm, CDCl₃): 6.44 (m, 1H, CH); 3.05 (s, 2H, CH₂); 2.45 (s, 3H, CH₃); 2.20 (s, 3H, CH₃); 2.15 (s, 3H, CH₃).

Synthesis of 6H-6-(2,3,5-trimethyl-cyclopenta[b]thiophene)chlorodimethylsilane

A solution of 1.28 g (5 mmol) of 2,3,5-trimethyl-6H-cyclopenta[b]thiophene in 40 mL of Et₂O was treated at −70° C. with 3.13 mL (5 mmol) of a 1.6 M solution of n-BuLi. After the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to −70° C. and treated with a solution of 1.30 g (10 mmol) of Me₂SiCl₂ in 10 mL of ether. When the addition was completed, the mixture was allowed to reach room temperature and stirred overnight. The resulting reaction mixture was filtered to remove LiCl and solvent was removed under reduced pressure. The crude product was used as such in the next step without further purification.

¹H-NM (δ, ppm, C₆D₆): 6.30 (s, 1H, CH); 3.25 (s, 1H, CH); 2.20 (s, 3H, CH₃); 2.10 (s, 3H, CH₃); 1.90 (s, 3H, CH₃); 0.30 (s, 3H, Si—CE₃); −0.10 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{6-(2,3,5-trimethyl-cyclopenta[b]thiophene)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-27

A suspension of 0.9 g (4.4 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 20 mL of ether was treated at −70° C. with 2.75 mL of a 1.6 M n-BuLi solution (4.4 mmol). After the addition, the resulting mixture was allowed to warm to room temperature and stirred for additional 50 min at this temperature. Then it was cooled again to −70° C. and added of an etheral solution (10 mL) of 6H-6-(2,3,5-trimethyl-cyclopenta[b]thiophene)chlorodimethylsilane coming from the previous step. The mixture was allowed to warm to room temperature and stirred overnight. The ligand 6-{(2,3,5-trimethyl-cyclopenta[b]thiophene)}-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]dithiophene)}dimethylsilane so-obtained was characterized by ¹H-NMR. ¹H-NMR (δ, ppm, C₆D₆): 6.70 (m, 2H, CH); 6.50 (s, 1H, CH); 4.40 (s, 1H, CH); 4.10 (s, 1H, CH); 2.39 (m, 3H, CH₃); 2.37 (d, 6H, CH₃); 2.25 (s, 3H, CH₃); 2.14 (s, 3H, CH₃); 0.18 (s, 3H, Si—CH₃); 0.07 (s, 3H, Si—CH₃).

The ligand was not isolated: its solution was treated at −70° C. with 5.60 mL of a 1.6 M n-BuLi solution (9.0 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.17 g (5 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.62 g (60% with respect to Me₂Th). The desired title compound was characterized by ¹H-NMR spectroscopy.

Example 27 Synthesis of 3-chloro-2-methyl-3-phenyl-2-propenal

1.2 mol (110 mL) of POCl₃ was added at 0° C. to a 2.8 mol (216 mL) of DMF (excess of DMF used as solvent). At the end of the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to 0° C. and treated with 1 mol (134 g) of propiophenone. The resulting reaction mixture was allowed to reach room temperature and stirred overnight. Then it was poured into a mixture of ice and water, added of sodium acetate and extracted with CHCl₃ (3×150 mL). The organic phase was separated, washed with water until neutral pH, dried over MgSO₄ and evaporated off to dryness. The residue was distilled in vacuo, b.p. 120° C./10 torr. Yield 163 g (90%).

¹H-NMR (δ, ppm, CDCl₃): 9.52 (s, 1H, CHO); 7.45 (m, 5H, CH); 2.12 (s, 3H, CH₃).

Synthesis of 4-methyl-5-phenyl-2-thiophene-ethylcarboxylate

Ethyl-2-mercaptoacetate (0.9 mol, 100 mL) was added at 0° C. to a solution of sodium ethoxide (1 mol, 68 g) in 500 mL of ethanol and the resulting mixture was stirred at the same temperature for 30 min. Then 3-chloro-2-methyl-3-phenyl-2-propenal (0.9 mol, 163 g) was added and stirring was continued overnight. The resulting product was diluted in 1.5 L of water, the organic layer was collected and the water layer was extracted with CH₂Cl₂ (4×150 mL). The combined organic layers were dried over MgSO₄, evaporated off to dryness and the residue was used in the next step without further purification. The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of 4-methyl-5-phenyl-2-thiophenecarboxylic acid

The 4-methyl-5-phenyl-2-thiophene-ethylcarboxylate coming from the previous step was added to a 30% solution of sodium hydroxide in 1 L of ethanol and the resulting mixture was refluxed for 2 h. Then it was diluted in water and extracted with 200 mL of benzene. The water phase was isolated, acidified and the mixture was filtered. The precipitate was dried under P₂O₅. Yield 127 g (65% with respect to 03-chloro-2-methyl-3-phenyl-2-propenal).

¹H-NMR (δ, ppm, CDCl₃): 7.75 (s, 1H, CH); 7.50–7.40 (m, 5H, CH); 2.37 (s, 3H, CH₃).

Synthesis of 3-methyl-2-phenylthiophene

The 4-methyl-5-phenyl-2-thiophenecarboxylic acid (127 g, 0.58 mol) prepared as described above was heated to 220–230° C. until the evolution of carbon dioxide ceased. The product was collected and distilled, b.p. 120° C./10 torr. Yield 30.3 g (30%).

¹H-NMR (δ, ppm, CDCl₃): 7.60 (d, 2H, CH); 7.48 (t, 2H, CH); 7.35 (t, 1H, CH); 7.25 (d, 1H, CH); 6.98 (d, 1H, CH); 2.39 (s, 3H, CH₃).

Synthesis of 2-formyl-4-methyl-5-phenylthiophene

0.35 mol (32 mL) of POCl₃ was added at 0° C. to a 1.0 mol (77 mL) of DMF (excess of DMF used as solvent). At the end of the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to 0° C. and treated with 3-methyl-2-phenylthiophene (60 g, 0.35 mol). The resulting reaction mixture was allowed to reach room temperature and after 12 h stirring at the same temperature was heated at 80° C. for 2 days. Then it was poured into a mixture of ice and water, added of sodium acetate and extracted with CHCl₃ (3×150 mL). The organic phase was separated, washed with water until neutral pH, dried over MgSO₄ and evaporated off to dryness. The residue was crystallized. Yield 60.2 g (85%).

¹H-NMR (δ, ppm, CDCl₃): 9.88 (s, 1H, CHO); 7.62 (s, 1H, CH); 7.55–7.40 (m, 5H, CH); 2.39 (s, 3H, CH₃).

Synthesis of 2-methyl-3-(4-methyl-5-phenyl-2-thienyl)-acrylic acid

A mixture of 2-formyl-4-methyl-5-phenylthiophene (20.2 g, 0.1 mol) and ethyl-2-bromopropionate (0.12 mol, 15.5 mL) was added to a suspension of Zn (7 g, 0.1 mol) in 150 mL of benzene with a catalytic amount of HgBr₂. The resulting mixture was refluxed under stirring while all amount of Zn will not be dissolved, and subsequently dissolved in water. The organic layer was isolated, washed with a 10% aq. solution of HCl, dried over MgSO₄ and evaporated off to dryness. The residue, corresponding to 2-methyl-3-(4-methyl-5-phenyl-2-thienyl)ethyl acrylate, was used without further purification in the synthesis of the related acid. In fact, it was added to a 30% aq. solution of sodium hydroxide in 100 mL of ethanol and refluxed for 2 h. The resulting reaction mixture was diluted in water, acidified and filtered. The precipitate was dried under P₂O₅. Yield 16.7 g (65%).

¹H-NMR (δ, ppm, CDCl₃): 7.90 (s, 1H, CH); 7.50–7.30 (m, 5H, CH); 7.20 (s, 1H, CH); 2.40 (s, 3H, CH₃); 2.20 (s, 3H, CH₃).

Synthesis of 2-methyl-3-(4-methyl-5-phenyl-2-thienyl)-2-propanoic acid

The desired 2-methyl-3-(4-methyl-5-phenyl-2-thienyl)-2-propanoic acid was obtained by electrochemical reduction of 2-methyl-3-(4-methyl-5-phenyl-2-thienyl)acrylic acid. Yield≈100%.

¹H-NMR (δ, ppm, CDCl₃): 7.50–7.30 (m, 5H, CH); 6.70 (s, 1H, CH); 3.30 (dd, 1H, CH); 2.90 (m, 2H, CH₂); 2.30 (s, 3H, CH₃); 1.30 (d, 3H, CH₃).

Synthesis of 3,5-dimethyl-2-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophene4-one

A solution of 3 g of P₂O₅ (21 mmol) in 30 mL of methanesulfonic acid (0.46 mol) was heated at 80° C. under stirring. A solution of 2-methyl-3-(4-methyl-5-phenyl-2-thienyl)-2-propanoic acid (65 mmol, 16.9 g) in 20 mL of CH₂Cl₂ was added and the resulting reaction mixture was stirred at the same temperature for 1.5 h. Then it was poured into a mixture of ice and water and stirred vigorously. The water layer was extracted with CH₂Cl₂ (3×50 mL), the organic layers were collected, washed with a 10% aqueous solution of sodium carbonate until neutral pH and finally with water. Then the organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. Yield 6.3 g (40%).

¹H-NMR (δ, ppm, CDCl₃): 7.50–7.40 (m, 5H, CH); 3.40 (dd, 1H, CH₂); 3.05 (m, 1H, CH); 2.80 (dd, 1H, CH₂); 2.55 (s, 3H, CH₃); 1.40 (d, 3H, CH₃).

Synthesis of 3,5-dimethyl-2-phenyl-6H-cyclopenta[b]thiophene (or 3,5-dimethyl-2-phenyl-1-thiopentalene)

A solution of 3,5-dimethyl-2-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one (6.3 g, 26 mmol) in 75 mL of ether was slowly added to a solution of LiAlH₄ (0.5 g, 13 mmol) in 50 mL of ether and stirred overnight. The resulting suspension was poured into a mixture of ice and water, the organic layer was isolated, while the water layer was extracted with ether (3×50 mL). The combined organic layers were washed with water, dried over MgSO₄ and evaporated off to dryness.

The 3,5-dimethyl-2-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ol so obtained was dissolved in 100 mL of benzene, added of 1 g of p-toluenesulfonic acid and was refluxed for 10 min. Then the reaction mixture was cooled to room temperature and treated with a saturated aqueous solution of Na₂CO₃. The organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. Yield 4.66 g (80% based on the starting ketone).

¹H-NMR (δ, ppm, CDCl₃): 7.50–7.40 (m, 5H, CH); 6.50 (q, 1H, CH); 3.20 (d, 1H, CH₂); 2.60 (dd, 1H, CH₂); 2.20 (s, 3H, CH₃); 1.66 (s, 3H, CH₃).

Synthesis of 6H-6-(2-phenyl-3,5-dimethyl-cyclopenta[b]thiophene)chloro dimethylsilane

A solution of 1.70 g (7.5 mmol) of 3,5-dimethyl-2-phenyl-6H-cyclopenta[b]thiophene in 40 mL of Et₂O was treated at −70° C. with 5.0 mL (8 mmol) of a 1.6 M solution of n-BuLi. After the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to −70° C. and treated with a solution of 1.30 g (10 mmol) of Me₂SiCl₂ in 10 mL of ether. When the addition was completed, the mixture was allowed to reach room temperature and stirred overnight. The resulting reaction mixture was filtered to remove LiCl and solvent was removed under reduced pressure. The crude product was used as such in the next step without further purification.

¹H-NMR (δ, ppm, C₆D₆): 7.60–7.20 (m, 5H, CH); 6.50 (m, 1H, CH); 3.40 (s, 1H, CH); 2.84 (s, 3H, CH₃); 2.21 (s, 3H, CH₃); 0.39 (s, 3H, Si—CH₃); 0.12 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{6-(2-phenyl-3,5-dimethyl-cyclopenta[b]thiophene)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-29

A suspension of 1.3 g (6.3 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 30 mL of ether was treated at −70° C. with 4.0 mL of a 1.6 M n-BuLi solution (6.4 mmol). After the addition, the resulting mixture was allowed to warm to room temperature and stirred for additional 50 min at this temperature. Then it was cooled again to −70° C. and added of an etheral solution (10 mL) of 6H-6-(3,5-dimethyl-2-phenyl-cyclopenta[b]thiophene)chlorodimethylsilane coming from the previous step. The mixture was allowed to warm to room temperature and stirred overnight. The ligand 6-{(3,5-dimethyl-2-phenyl-cyclopenta[b]thiophene)}-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}dimethylsilane so-obtained was characterized by ¹H-NMR.

¹H-NMR (δ, ppm, C₆D₆): 7.60–7.10 (m, 5H, CH); 6.85 (s, 1H, CH); 6.80 (s, 1H, CH); 6.50 (m, 1H, CH); 4.37 (s, 1H, CH); 4.10 (s, 1H, CH); 2.38 (d, 3H, CH₃); 2.37 (d, 3H, CH₃); 2.36 (s, 3H, CH₃); 2.12 (s, 3H, CH₃); −0.05 (s, 3H, Si—CH₃); −0.16 (s, 3H, Si—CH₃).

The ligand was not isolated: its solution was treated at −70° C. with 8.2 mL of a 1.6 M n-BuLi solution (13.1 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.51 g (6.5 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the yellow-brown precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 2.30 g (56% with respect to Me₂Th). The desired title compound was characterized by ¹H-NMR.

¹H-NMR (δ, ppm, CD₂Cl₂): 7.44–7.36 (m, 5H, CH); 6.86 (q, 1CH, J=1.24 Hz); 6.73 (q, 1H, CH, J=1.24 Hz); 6.56 (bs, 1H, CH); 2.63 (d, 3H, CH₃, J=1.24 Hz); 2.50 (d, 3H. CH₃, J=1.24 Hz); 2.35 (s, 3H, CH₃); 2.20 (s, 3H, CH₃); 1.22 (s, 3H, Si—CH₃); 1.14 (s, 3H, Si—CH₃).

Example 28 Synthesis of 3-chloro-2,3-diphenyl-2-propenal

0.25 mol (23 mL) of POCl₃ was added at 0° C. to a 0.3 mol (23.5 mL) of DMF. At the end of the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to 0° C. and treated with 0.1 mol (19.6 g) of deoxybenzoin. The resulting reaction mixture was allowed to reach room temperature, stirred for 12 h at the same temperature and subsequently heated at 100° C. for 2 h. Finally it was poured into a mixture of ice and 10% solution of sodium acetate in water. The oily precipitate was filtered and washed with cold methanol and hexane. The residue was crystallized. Yield 18.5 g (76%).

¹H-NMR (δ, ppm, CDCl₃): 9.70 (s, 1H, CHO); 7.60–7.20 (m, 10H, CH).

Synthesis of 4,5-diphenyl-2-thiophene-ethylcarboxylate

Ethyl-2-mercaptoacetate (40 mmol, 4.4 mL) was added at 0° C. to a solution of sodium ethoxide (42 mmol, 2.86 g) in 50 mL of ethanol and the resulting mixture was stirred at the same temperature for 30 min. Then 3-chloro-2,3-diphenyl-2-propenal (37 mmol, 9.0 g) was added and stirring was continued overnight. The resulting orange suspension was heated at 50° C. for 2 h, then cooled to room temperature and diluted in 100 mL of water. The so-obtained red solution containing a precipitate was extracted with Et₂O (3×50 mL). The combined organic layers were washed with NH₄Cl/water, dried over MgSO₄ and evaporated off to dryness. The solid residue was recrystallized from hexane. Yield 9.2 g (81%).

¹H-NMR (δ, ppm, CDCl₃): 7.40–7.30 (m, 11H, CH); 4.40 (q, 2H, CH₂); 1.40 (t, 3H, CH₃).

Synthesis of 4,5-diphenyl-2-thiophenecarboxylic acid

The 4,5-diphenyl-2-thiophene-ethylcarboxylate (3.6 g, 12 mmol) coming from the previous step was added to a 30% solution of sodium hydroxide in 20 mL of ethanol and the resulting mixture was refluxed for 2 h. Then it was diluted in water and the water phase was acidified. The white precipitate obtained was filtered and dried at 80° C. Yield 3.16 g (94%).

¹H-NMR (δ, ppm, (CD₃)₂SO): 7.80 (s, 1H, CH); 7.40–7.30 (m, 10H, CH).

Synthesis of 2,3-diphenylthiophene

The 4,5-diphenyl-2-thiophenecarboxylic acid (28 g, 0.1 mol) prepared as described above was heated to 220–230° C. until the evolution of carbon dioxide ceased. The residue was diluted in water and extracted with 100 mL of benzene. The organic phase was dried over MgSO₄ and evaporated off to give the crystallized product. Yield 22.45 g (95%).

¹H-NMR (δ, ppm, CDCl₃): 7.35 (d, 1H, CH); 7.34–7.26 (m, 10H, CH); 7.19 (d, 1H, CH).

Synthesis of 2-formyl-4,5-diphenylthiophene

POCl₃ (80 mmol, 7.32 mL) was added at 0° C. to a solution of 2,3-diphenylthiophene (18 g, 76 mmol) in DMF (18 mL, 0.23 mol). At the end of the addition, the reaction mixture was allowed to warm to room temperature and refluxed for 3 h. Then it was cooled to room temperature and poured into a mixture of ice and a 10% solution of sodium hydroxide in water. The oily precipitate obtained was filtered and washed with cold methanol and hexane. The residue was crystallized. Yield 15 g (75%).

¹H-NMR (δ, ppm, CDCl₃): 9.95 (s, 1H, CHO); 7.82 (s, 1H, CH); 7.40–7.25 (m, 10H, CH).

Synthesis of 2-methyl-3-(4,5-diphenyl-2-thienyl)-ethyl acrylate

A mixture of 2-formyl-4,5-diphenylthiophene (14.8 g, 56 mmol) and ethyl-2-bromopropionate (60 mmol, 7.8 mL) was added to a suspension of Zn (4.25 g, 65 mmol) in 100 mL of benzene with a catalytic amount of I₂. The resulting mixture was refluxed under stirring while all amount of Zn will not be dissolved, and subsequently dissolved in water. The organic layer was isolated, washed with a 10% aq. solution of HCl, dried over MgSO₄ and evaporated off to dryness. The residue was dissolved into 50 mL of benzene and was refluxed with 0.5 g of p-toluenesulfonic acid for 1 h. Then the reaction mixture was cooled to room temperature and treated with a saturated aqueous solution of Na₂CO₃. The organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. Yield 17.6 g (90%).

¹H-NMR (δ, ppm, CDCl₃): 7.90 (s, 1H, CH); 7.40–7.25 (m, 11H, CH); 4.30 (q, 2H, CH₂); 2.30 (d, 3H, CH₃); 1.40 (t, 3H, CH₃).

Synthesis of 2-methyl-3-(4,5-diphenyl-2-thienyl)-acrylic acid

The 2-methyl-3-(4,5-diphenyl-2-thienyl)-ethyl acrylate (18.9 g, 54 mmol), coming from the previous step, was added to a 30% aq. solution of sodium hydroxide in 300 mL of ethanol and refluxed for 2 h. The resulting reaction mixture was diluted in water, acidified and filtered. The precipitate was dried under P₂O₅. Yield 12.1 g (70%).

¹H-NMR (δ, ppm, (CD₃)₂SO): 7.85 (d, 1H, CH); 7.55 (s, 1H, CH); 7.40–7.20 (m, 10H, CH); 2.15 (s, 3H, CH₃).

Synthesis of 2-methyl-3-(4,5-diphenyl-2-thienyl)-2-propanoic acid

The desired 2-methyl-3-(4,5-diphenyl-2-thienyl)-2-propanoic acid was obtained by electrochemical reduction of 2-methyl-3-(4,5-diphenyl-2-thienyl)-acrylic acid. Yield≈100%.

¹H-NMR (δ, ppm, (CD₃)₂SO): 7.30–7.15 (m, 10H, CH); 6.90 (s, 1H, CH); 3.10 (dd, 1H, CH); 2.70 (m, 2H, CH₂); 1.10 (d, 3H, CH₃).

Synthesis of 5-methyl-2,3-diphenyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one

A solution of P₂O₅ (2.6 g, 18 mmol) in 15 mL of methanesulfonic acid (0.23 mol) was heated at 80° C. under stirring. A solution of 2-methyl-3-(4,5-diphenyl-2-thienyl)-2-propanoic acid (18 mmol, 6.0 g) in 20 mL of CH₂Cl₂ was added and the resulting reaction mixture was stirred at the same temperature for 15 min. Then it was poured into a mixture of ice and water and stirred vigorously. The water layer was extracted with CH₂Cl₂ (3×50 mL), the organic layers were collected, washed with a 10% aqueous solution of sodium carbonate until neutral pH and finally with water. Then the organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. The residue was passed through a column packed with silica gel 60 by using a mixture hexane/ethyl acetate=5/1 as eluent. The evaporation of the red fraction was given the crystallized product. Yield 2.18 g (40%).

¹H-NMR (δ, ppm, CDCl₃): 7.40–7.20 (m, 10H, CH); 3.50 (dd, 1H, CH₂); 3.05 (m, 1H, CH); 2.85 (dd, 1H, CH₂); 1.40 (d, 3H, CH₃).

Synthesis of 5-dimethyl-2,3-diphenyl-6H-cyclopenta[b]thiophene (or 5-dimethyl-2,3-diphenyl-1-thiopentalene)

A solution of 5-methyl-2,3-diphenyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one (6.08 g, 20 mmol) in 75 mL of ether was slowly added to a solution of LiAlH₄ (0.38 g, 10 mmol) in 50 mL of ether and stirred overnight. The resulting suspension was poured into a mixture of ice and water, the organic layer was isolated, while the water layer was extracted with ether (3×50 mL). The combined organic layers were washed with water, dried over MgSO₄ and evaporated off to dryness. The 5-methyl-2,3-diphenyl-5,6-dihydro-4H-cyclopenta[b]thiophen -4-ol so obtained was dissolved in 100 mL of benzene, added of 1 g of p-toluenesulfonic acid and was refluxed for 10 min. Then the reaction mixture was cooled to room temperature and treated with a saturated aqueous solution of Na₂CO₃. The organic phase was isolated, dried over MgSO₄ and evaporated off to dryness giving the crystallized product. Yield 3.46 g (60% with respect to the starting ketone).

¹H-NMR (δ, ppm, CDCl₃): 7.40–7.20 (m, 10H, CH); 6.48 (q, 1H, CH); 3.24 (s, 2H, CH₂); 2.24 (d, 3H, CH₃).

Synthesis of 6H-6-(5-methyl-2,3-diphenyl-cyclopenta[b]thiophene)chloro dimethylsilane

A solution of 1.28 g (4.4 mmol) of 5-methyl-2,3-diphenyl-6H-cyclopenta[b]thiophene in 40 mL of Et₂O was treated at −70° C. with 3.5 mL (5.6 mmol) of a 1.6 M solution of n-BuLi. After the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to −70° C. and treated with a solution of 1.30 g (10 mmol) of Me₂SiCl₂ in 10 mL of ether. When the addition was completed, the mixture was allowed. to reach room temperature and stirred overnight. The resulting reaction mixture was filtered to remove LiCl and the solvent was removed under reduced pressure. The crude product was used as such in the next step without further purification.

¹H-NMR (δ, ppm, C₆D₆): 7.60–7.00 (m, 10H, CH); 6.56 (m, 1H, CH); 3.40 (s, 1H, CH); 2.13 (s, 3H, CH₃); 0.37 (s, 3H, Si—CH₃); 0.15 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{6-(5-methyl-2,3-diphenyl-cyclopenta[b]thiophene)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-30

A suspension of 0.9 g (4.4 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 30 mL of ether was treated at −70° C. with 3.0 mL of a 1.6 M n-BuLi solution (4.8 mmol). After the addition, the resulting mixture was allowed to warm to room temperature and stirred for additional 50 min at this temperature. Then it was cooled again to −70° C. and added of an etheral solution (10 mL) of 6H-6-(5-methyl-2,3-diphenyl-cyclopenta[b]thiophene)chlorodimethylsilane coming from the previous step. The mixture was allowed to warm to room temperature and stirred overnight. The ligand 6-{(5-methyl-2,3-diphenyl-cyclopenta[b]thiophene)}-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}dimethylsilane so-obtained was characterized by ¹H-NMR.

¹H-NMR (δ, ppm, C₆D₆): 7.60–7.00 (m, 10H, CH); 6.85 (m, 1H, CH); 6.80 (m, 1H, CH); 6.60 (m, 1H, CH); 4.35 (s, 1H, CH); 4.10 (s, 1H, CH); 2.40 (d, 3H, CH₃); 2.38 (d, 3H, CH₃); 2.05 (s, 3H, CH₃); 0.05 (s, 3H, Si—CH₃); −0.20 (s, 3H, Si—CH₃).

The ligand was not isolated: its solution was treated at −70° C. with 5.6 mL of a 1.6 M n-BuLi solution (9.0 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.17 g (5.0 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.46 g (47% with respect to Me₂Th).

¹H-NMR (δ, ppm, CD₂Cl₂): 7.39–7.24 (m, 10H, CH); 6.88 (q, 1H, CH, J=1.17 Hz); 6.76 (q, 1H, CH, J=1.17 Hz); 6.59 (bs, 1H, CH); 2.63 (d, 3H, CH₃, J=1.17 Hz); 2.51 (d, 3H, CH₃, J=1.17 Hz); 2.35 (s, 3H, CH₃); 1.25 (s, 3H, Si—CH₃); 1.16 (s, 3H, Si—CH₃).

Example 29 Synthesis of 3-chloro-2-phenyl-2-butenal

0.375 mol (35 mL) of POCl₃ was added at 0° C. to a 0.45 mol (35 mL) of DMF. At the end of the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to 0° C. and carefully treated with 0.15 mol (20.1 g) of phenylacetone. The resulting reaction mixture was stirred at the same temperature for 1 h. Then it was poured into a mixture of ice and water, added of sodium acetate and extracted with CHC₃ (3×50 mL). The organic phase was separated, washed with water until neutral pH, dried over MgSO₄ and carefully evaporated off to dryness. The residue was distilled in vacuo, b.p. 90–110° C./0.21 torr.

Yield 10 g (37%). ¹H-NMR (δ, ppm, CDCl₃): 10.50 (s, 1H, CHO); 7.40–7.00 (m, 5H, CH); 2.20 (s, 3H, CH₃).

Synthesis of 5-methyl-4-phenyl-2-thiophene-ethylcarboxylate

Ethyl-2-mercaptoacetate (45.8 mmol, 5 mL) was added at 0° C. to a solution of sodium ethoxide (46 mmol, 3.13 g) in 50 mL of ethanol and the resulting mixture was stirred at the same temperature for 30 min. Then 3-chloro-2-phenyl-2-butenal (45.8 mmol, 8.27 g) was added and stirring was continued overnight. The resulting product was refluxed for 2 h, cooled to room temperature and diluted in 100 mL of water. The organic layer was collected and the water layer was extracted with CH₂Cl₂ (3×50 mL). The combined organic layers were dried over MgSO₄, evaporated off to dryness and the residue was used in the next step without further purification. The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of 5-methyl-4-phenyl-2-thiophenecarboxylic acid

The 5-methyl-4-phenyl-2-thiophene-ethylcarboxylate coming from the previous step was added to a 30% solution of sodium hydroxide in 100 mL of ethanol and the resulting mixture was refluxed for 2 h. Then it was diluted in water and extracted with 50 mL of benzene. The water phase was isolated, acidified and the mixture was filtered. The precipitate was dried under P₂O₅. Yield 9.5 g (95% based on 3-chloro-2-phenyl-2-butenal).

¹H-NMR (δ, ppm, CDCl₃): 12.00 (s, 1H, COOH); 7.90 (s, 1H, CH); 7.50–7.40 (m, 5H, CH); 2.55 (s, 3H, CH3).

Synthesis of 2-methyl-3-phenylthiophene

The 5-methyl-4-phenyl-2-thiophenecarboxylic acid (54 g, 0.25 mol) prepared as described above was heated to 220–230° C. until the evolution of carbon dioxide ceased. The product was collected and distilled, b.p. 117° C./10 torr. Yield 30 g (70%).

¹H-NMR (δ, ppm, CDCl₃): 7.45 (m, 5H, CH); 7.15 (d, 1H, CH); 7.10 (d, 1H, CH); 2.55 (s, 3H, CH₃).

Synthesis of 2-formyl-5-methyl-4-phenylthiophene

0.166 mol (15 mL) of POCl₃ was added at 0° C. to a 0.5 mol (39 mL) of DMF. At the end of the addition, the mixture was allowed to warm to room temperature and stirred for 1 h. Then it was cooled again to 0° C. and treated with 2-methyl-3-phenylthiophene (29 g, 0.166 mol). The resulting reaction mixture was allowed to reach room temperature and after 12 h stirring at the same temperature was heated at 80° C. for 2 days. Then it was poured into a mixture of ice and water and added of sodium acetate. The precipitate so obtained was filtered, washed with water and subsequently with hexane. The yellow powder was dried in vacuo.

Yield 27.7 g (83%). ¹H-NMR (δ, ppm, CDCl₃): 9.88 (s, 1H, CHO); 7.70 (s, 1H, CH); 7.55–7.40 (m, 5H, CH); 2.55 (s, 3H, CH₃).

Synthesis of 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)-ethyl acrylate

A mixture of 2-formyl-5-methyl-4-phenylthiophene (27.6 g, 0.136 mol) and ethyl-2-bromopropionate (0.14 mol, 18.2 mL) was added to a suspension of Zn (9.8 g, 0.15 mol) in 250 mL of benzene with a catalytic amount of I₂. The resulting mixture was refluxed under stirring while all amount of Zn will not be dissolved, and subsequently dissolved in water. The organic layer was isolated, washed with a 10% aq. solution of HCl, dried over MgSO₄ and evaporated off to dryness. The residue was used without further purification in the synthesis of the related acid. The title compound was characterized by ¹H-NMR spectroscopy.

Synthesis of 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)-acrylic acid

The 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)-ethyl acrylate coming from the previous step was added to a 30% aq. solution of sodium hydroxide in 200 mL of ethanol and refluxed for 2 h. The resulting reaction mixture was diluted in water, acidified and filtered. The precipitate was dried under P₂O₅. Yield 26.0 g (74% based on 2-formyl-5-methyl-4-phenylthiophene).

¹H-NMR (δ, ppm, CDCl₃): 7.90 (s, 1H, CH); 7.50–7.30 (m, 5H, CH); 7.25 (d, 1H, CH); 2.60 (s, 3H, CH₃); 2.25 (s, 3H, CH₃).

Synthesis of 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)-2-propanoic acid

The desired 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)-2-propanoic acid was obtained by electrochemical reduction of 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)acrylic acid. Yield≈100%.

¹H-NMR (δ, ppm, CDCl₃): 7.50–7.20 (m, 5H, CH); 6.80 (s, 1H, CH); 3.25 (dd, 1H, CH); 2.85 (m, 2H, CH₂); 2.50 (s, 3H, CH₃); 1.30 (d, 3H, CH₃).

Synthesis of 2,5-dimethyl-3-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one

A solution of 3 g of P₂O₅ (21 mmol) in 30 mL of methanesulfonic acid (0.46 mol) was heated at 80° C. under stirring. A solution of 2-methyl-3-(5-methyl-4-phenyl-2-thienyl)-2-propanoic acid (65 mmol, 16.9 g) in 20 ml, of CH₂Cl₂ was added and the resulting reaction mixture was stirred at the same temperature for 1.5 h. Then it was poured into a mixture of ice and water and stirred vigorously. The water layer was extracted with CH₂Cl₂ (3×50 mL), the organic layers were collected, washed with a 10% aqueous solution of sodium carbonate until neutral pH and finally with water. Then the organic layers were collected, dried over MgSO₄ and evaporated off to dryness. The residue was passed through a column packed with silica gel 60 by using a mixture of hexane/ethyl acetate=3/1 as eluent. The evaporation of the red fraction was given the oily product. Yield 4.4 g (28%).

¹H-NMR (δ, ppm, CDCl₃): 7.50–7.40 (m, 5H, CH); 3.42 (dd, 1H, CH₂); 3.02 (m, 1H, CH); 2.79 (dd, 1H, CH₂); 2.50 (s, 3H, CH₃); 1.35 (d, 3H, CH₃).

Synthesis of 2,5-dimethyl-3-phenyl-611-cyclopenta[b]thiophene (or 2,5-dimethyl-3-phenyl-1-thiopentalene)

A solution of 2,5-dimethyl-3-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophene-4-one (4.4 g, 18 mmol) in 50 mL of ether was slowly added to a solution of LiAlH₄ (0.35 g, 9 mmol) in 50 mL of ether and stirred overnight. The resulting suspension was poured into a mixture of ice and water, the organic layer was isolated, while the water layer was extracted with ether (3×50 mL). The combined organic layers were washed with water, dried over MgSO₄ and evaporated off to dryness. The 2,5-dimethyl-3-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ol so obtained was dissolved in 100 mL of benzene, added of 1 g of p-toluenesulfonic acid and was refluxed for 10 min. Then the reaction mixture was cooled to room temperature and treated with a saturated aqueous solution of Na₂CO₃. The organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. The residue was passed through a column packed with Al₂O₃ by using hexane as eluent. The evaporation of the yellow fraction was given the crystallized product. Yield 1.5 g (37% based on the starting ketone).

¹H-NMR (δ, ppm, CDCl₃): 7.50–7.40 (m, 5H, CH); 6.52 (q, 1H, CH); 3.24 (d, 1H, CH₂); 2.60 (d, 1H, CH₂); 2.24 (dd, 3H, CH₃); 1.66 (s, 3H, CH₃).

Synthesis of 6H-6-(2,5-dimethyl-3-phenyl-cyclopenta[b]thiophene)chloro dimethylsilane

A solution of 1.20 g (5.3 mmol) of 2,5-dimethyl-3-phenyl-6H-cyclopenta[b]thiophene in 40 mL of Et₂O was treated at −70° C. with 3.3 mL (5.3 mmol) of a 1.6 M solution of n-BuLi. After the addition, the mixture was allowed to warm to room temperature and stirred for1 h. Subsequently it was cooled again to −70° C. and treated with a solution of 1.30 g (10.1 mmol) of Me₂SiCl₂ in 10 mL of ether. When the addition was completed, the mixture was allowed to reach room temperature and stirred overnight. The resulting reaction mixture was filtered to remove LiCl and solvent was removed under reduced pressure. The crude product was used as such in the next step without further purification.

¹H-NMR (δ, ppm, C₆D₆): 7.45–7.20 (m, 5H, CH); 6.50 (m, 1H, CH); 3.40 (m, 1H, CH); 2.38 (s, 3H, CH₃); 2.12 (s, 3H, CH₃); 0.36 (s, 3H, Si—CH₃); 0.11 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{6-(2,5-dimethyl-3-phenyl-cyclopenta[b]thiophene)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)} zirconium dichloride C-33

A suspension of 0.9 g (4.4 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 30 mL of ether was treated at −70° C. with 3.0 mL of a 1.6 M n-BuLi solution (4.8 mmol). After the addition, the resulting mixture was allowed to warm to room temperature and stirred for additional 50 min at this temperature. Then it was cooled again to −70° C. and added of an etheral solution (10 mL) of 6H-6-(2,5-dimethyl-3-phenyl-cyclopenta[b]thiophene)chlorodimethylsilane coming from the previous step. The mixture was allowed to warm to room temperature and stirred overnight. The ligand 6-{(2,5-dimethyl-3-phenyl-cyclopenta[b]thiophene)}-7-{(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}dimethylsilane so-obtained was characterized by ¹H-NMR.

¹H-NMR (δ, ppm, CDCl₃): 7.45–7.20 (m, 5H, CH); 6.85 (s, 1H, CH_();) 6.80 (s, 1H, CH); 6.60 (m, 1H, CH); 4.30 (s, 1H, CH); 4.00 (s, 1H, CH); 2.70 (d, 3H, CH3); 2.65 (d, 3H, CH₃); 2.60 (s, 3H, CH₃); 2.30 (s, ₃H, CH₃); −0.18 (s, 3H, Si—CH3); −0.30 (s, 3H, Si—CH₃).

The ligand was not isolated: its solution was treated at −70° C. with 5.6 mL of a 1.6 M n-BuLi solution (9.0 mmol). Then the reaction mixture was allowed to reach room temperature and stirred for 1 h. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.17 g (5.0 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the yellow precipitate was filtered, washed twice with ether, dried and finally recrystallized from CH₂Cl₂. Yield 1.68 g (59% with respect to Me₂Th). The desired title compound was characterized by ¹H-NMR spectroscopy.

Example 30 Synthesis of 1-bromo-2-(3-indenyl)ethane

A 1.6 M n-BuLi solution in hexane (100 mL, 0.16 mol) was added at 0° C. to a solution of indene (18.6 g, MW=116.16, 0.16 mol) in 300 mL of ether. The resulting suspension was allowed to warm to room temperature and stirred for 4 h at the same temperature. Then the indenyl lithium suspension was cooled again to −50° C. and added of a solution of 1,2-dibromoethane (0.24 mol, 21 mL) in 50 mL of ether. The reaction mixture was allowed to warm up slowly to room temperature and stirred overnight. Then it was treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated, evaporated off to dryness and distilled in vacuo, b.p. 110° C./0.5 torr. Yield 21.6 g (60%). The title compound was characterized by NMR spectroscopy.

Synthesis of 1,2-(3-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)ethane

A solution of 2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene (1.03 g, 5 mmol) in 50 mL of THF was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (3.1 mL, 5 mmol). The resulting mixture was stirred for additional 45 min at 0° C., then cooled again to −70° C. and treated with 1-bromo-2-(3-indenyl)ethane (1.12 g, 5 mmol) in 25 mL of THF. The reaction mixture was allowed to warm to room temperature and subsequently treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated and the solvents were removed. The residue was passed through a column packed with silica gel by using hexane as eluent. Yield 1.26 g (72%). The title compound was characterized by NMR spectroscopy.

Synthesis of ethylidene{(1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-37

A solution of 1,2-(3-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)ethane (1.26 g, 3.62 mmol) in 15 mL of ether and 60 mL of hexane was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (4.7 mL, 7.5 mmol). The resulting suspension was stirred for additional 2 h at room temperature, then cooled again to −70° C. and added of ZrCl₄ (0.94 g, 4 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight. The dark orange precipitate was filtered, washed twice with ether, dried and then recrystallyzed from CH₂Cl₂. Yield 0.92 g (50%).

¹H-NMR (δ, ppm, CD₂Cl₂): 7.70 (dd, 1H, CH); 7.45 (dd, 1H, CH); 7.20 (m, 1H, CH); 7.10 (m, 1H, CH); 6.75 (q, 1H, CH); 6.60 (q, 1H, CH); 6.55 (dd, 1H, CH); 6.40 (d, 1H, CH); 3.95–3.80 (m, 2H, CH₂); 3.65–3.55 (m, 2H, CH₂); 2.60 (d, 3H, CH₃); 2.45 (d, 3H, CH₃).

Example 31 Synthesis of chloro(4,7-dimethyl-1-indenyl)dimethylsilane

The precursor 4,7-dimethylindene was prepared by following standard procedure (as reported in Tetrahedron, 51, (1995), 4347).

A 1.6 M n-BuLi solution in hexane (62.5 mL, 0.1 mol) was added at 0° C. to a solution of 4,7-dimethylindene (14.42 g, MW=144.22, 0.1 mol) in 200 mL of hexane and 50 mL of THF. The resulting suspension was allowed to warn to room temperature and stirred for 4 h at the same temperature. Then the indenyl lithium suspension was cooled again to −50° C. and added of a solution of dichlorodimethylsilane (0.2 mol, 24 mL) in 50 mL of THF. The resulting suspension was allowed to warm to room temperature and stirred overnight. The precipitate of lithium chloride was filtered, the filtrate was evaporated off to dryness and distilled in vacuo, b.p. 98° C. 0.5 torr. Yield 16.5 g (70%). The title compound was characterized by NMR spectroscopy.

Synthesis of (4,7-dimethyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A solution of 2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene (1.90 g, 9.2 mmol) in 50 mL of ether was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (5.8 mL, 9.2 mmol). The resulting mixture was stirred for additional 45 min at 0° C., then cooled again to −70° C. and treated with chloro(4,7-dimethyl-1-indenyl)dimethylsilane (2.18 g, 9.2 mmol) in 10 mL of ether. The reaction mixture was allowed to warm to room temperature and subsequently treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated and the solvents were removed. The residue was recrystallysed from hexane. Yield 3.67 g (98%).

¹H-NMR (δ, ppm, CDCl₃): 7.07 (dd, 1H, CH); 7.05 (d, 1H, CH); 6.95 (d, 1H, CH); 6.90 (m, 2H, CH); 6.60 (dd, 1H, CH); 4.00 (s, 1H, CH); 3.85 (s, 1H, CH); 2.64 (s, 3H, CH₃); 2.60 (s, 3H, CH₃); 2.50 (s, 3H, CH₃); 2.40 (s, 3H, CH₃); −0.20 (3H, Si—CH₃); −0.40 (s, 3H, Si—CH₃).

Synthesis of dimethylsily {(4,7-dimethyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-38

A solution of (4,7-dimethyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane (3.67 g, 9.02 mmol) in 15 mL of ether and 50 mL of hexane was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (12.5 mL, 20 mmol). The resulting suspension was stirred for additional 2 h at room temperature, then cooled again to −70° C. and added of ZrCl₄ (2.52 g, 10.8 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight. The yellow precipitate was filtered, washed twice with ether, dried and then recrystallyzed from CH₂Cl₂. Yield 3.57 g (70%). The title compound was characterized by NMR spectroscopy.

Example 32 Synthesis of-chloro(2,4,7-trimethyl-1-indenyl)dimethylsilane

The precursor 2,4,7-trimethylindene was prepared by following standard procedure (as reported in Eur. Pat. Appl. 0693506).

A 1.6 M n-BuLi solution in hexane (37.5 mL, 60 mmol) was added at 0° C. to a solution of 2,4,7-trimethylindene (9.5 g, MW=158.24, 60 mmol) in 200 mL of hexane and 50 mL of THF. The resulting suspension was allowed to warm to room temperature and stirred for 4 h at the same temperature. Then the indenyl lithium suspension was cooled again to −50° C. and added of a solution of dichlorodimethylsilane (90 mmol, 11 mL) in 50 mL of THF. The resulting suspension was allowed to warm to room temperature and stirred overnight. The precipitate of lithium chloride was filtered, the filtrate was evaporated off to dryness and distilled in vacuo, b.p. 110° C./0.5 torr. Yield 10.1 g (67%).

¹H-NMR (δ, ppm, C₆D₆): 6.75 (d, 1H, CH); 6.60 (d, 1H, CH); 6.30 (s, 1H, CH); 3.25 (s, 1H, CH); 2.25 (s, 3H, CH₃); 2.15 (s, 3H, CH₃); 2.10 (s, 3H, CH₃); −0.05 (s, 3H, Si—CH₃); −0.02 (s, 3H, Si—CH₃).

Synthesis of (2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A solution of 2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene (1.65 g, 8 mmol) in 50 mL of ether was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (5.0 mL, 8 mmol). The resulting mixture was sired for additional 45 min at 0° C., then cooled again to −70° C. and treated with chloro(2,4,7-trimethyl-1-indenyl)dimethylsilane (2.0 g, 8 mmol) in 20 mL of ether. The reaction mixture was allowed to warm to room temperature and subsequently treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated and the solvents were removed. Yield 3.36 g (˜100%).

¹H-NMR (δ, ppm, CDCl₃): 6.90 (d, 1H, CH); 6.80 (d, 1H, CH); 6.70 (m, 2H, CH); 6.65 (m, 1H, CH); 4.15 (s, 1H, CH); 4.00 (s, 1H, CH); 2.65 (s, 3H, CH₃); 2.63 (s, 3H, CH₃); 2.55 (s, 3H, CH₃); 2.50 (s, 3H, CH₃); 2.20 (s, 3H, CH₃); −0.15 (s, 3H, Si—CH₃); −0.30 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-39

A solution of (2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane (3.36 g, 8.0 mmol) in 80 mL of ether was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (12.5 mL, 20 mmol). The resulting suspension was stirred for additional 2 h at room temperature, then cooled again to −70° C. and added of ZrCl₄ (2.34 g, 10 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight. The orange precipitate was filtered, washed twice with ether, dried and then recrystallyzed from CH₂Cl₂. Yield 2.73 g (59%). The title compound was characterized by NMR spectroscopy. cl Example 33

Synthesis of 2-methyl-2,3-dihydro-1H-cyclopenta[a]naphtalen-1-one

To a suspension of AlCl₃ (85 g, 0.635 mol) in 200 mL of CH₂Cl₂ were added at 0° C. first naphalene (32.5 g, 0.254 mol) and then a solution of 2-methylacryloyl chloride (26.5 g, 0.254 mol) in 50 mL of CH₂Cl₂.The reaction mixture was stirred for 30 min at 0° C., then 2 h at room temperature and finally poured into a mixture of ice and water. The dark organic layer was separated, while the water layer was extracted with CHCl₃ (3×150 mL). The organic layers were collected, washed with potassium carbonate/water until neutral pH, dried over MgSO₄ and evaporated off to dryness. Yield 28.09 g (56%). The title compound was characterized by NMR spectroscopy.

Synthesis of 2-methyl-2,3-dihydro-1H-cyclopenta[a]naphtalen-1-ol

A solution of 2-methyl-2,3-dihydro-1H-cyclopenta[a]naphtalen-1-one (28.09 g, 0.143 mol) in 100 mL of THF was slowly added to a suspension of LiAlH₄ (2.18 g, 58 mmol) in 200 mL of ether and refluxed for 2 h under stirring. The reaction mixture was subsequently transferred into a 2-L beaker and slowly hydrolyzed, under constant stirring, by dropwise addition of a 10% aq. solution of HCl until pH 5. The organic layer was separated, while the water layer was extracted with ether (3×100 mL). The organic layers were collected, washed with potassium carbonate/water until neutral pH, dried over MgSO₄ and evaporated off to dryness. The so-obtained product, as a mixture of two isomers, was used in the next step without further purification.

Synthesis of 2-methyl-3H-cyclopenta[a]naphtalene

A mixture of 2-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ol (obtained as described above) and 1 g of p-toluenesulphonic acid in 200 mL of benzene was refluxed for 1 h. Then the reaction mixture was cooled to room temperature and treated with a saturated aqueous solution of Na₂CO₃. The organic phase was isolated, dried over MgSO₄ and evaporated off to dryness. Yield 14.2 g (55% based on starting 2-methyl-2,3-dihydro-1H-cyclopenta[a]naphtalen-1-one).

¹H-NMR (δ, ppm, CDCl₃): 8.10–7.40 (m, 6H, CH); 7.10 (m, 1H, CH); 3.50 (s, 2H, CH₂); 2.33 (s, 3H, CH₃).

Synthesis of chloro(2-methyl-3H-cyclopenta[a]naphthalen-3-yl)dimethylsilane

A 1.6 M n-BuLi solution in hexane (7.5 mL, 12 mmol) was added at −50° C. to a solution of 2-methyl-3H-cyclopenta[a]naphthalene (2.14 g, MW=180.25, 11.9 mmol) in 50 mL of ether. The resulting suspension was allowed to warm to room temperature and stirred for 45 min at the same temperature. Then the lithium suspension was cooled again to −70° C. and added of dichlorodimethylsilane (18 mmol, 2.2 mL). The reaction mixture was allowed to warm to room temperature and stirred overnight. The precipitate of lithium chloride was filtered, the filtrate was evaporated off to dryness and dried in vacuo. Yield 3.14 g (97%).

¹H-NMR (δ, ppm, C₆D₆): 8.10 (d, 1H, CH); 7.85 (d, 1H, CH); 7.50–7.40 (m, 4H, CH); 7.10 (s, 1H, CH); 3.55 (s, 1H, CH); 2.30 (s, 3H, CH₃); 0.22 (s, 3H, Si—CH₃); −0.05 (s, 3H, Si—CH₃).

Synthesis of (2-methylcyclopenta[a]naphthalen-3-yl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A solution of 2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene (2.37 g, 11.5 mmol) in 75 mL of ether was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (7.5 mL, 12 mmol). The resulting mixture was stirred for additional 45 min at 0° C., then cooled again to −70° C. and treated with chloro(2-methyl-3H-cyclopenta[a]naphthalen-3-yl)dimethylsilane (3.14 g, 11.5 mmol) in 25 mL of ether. The reaction mixture was allowed to warm to room temperature and subsequently treated with a saturated aqueous solution of NH₄Cl. The organic phase was isolated and the solvents were removed. The residue was passed through a short column packed with silica gel by using hexane as eluent. Yield 4.07 g (80%).

¹H-NMR (δ, ppm, CDCl₃): 8.20 (d, 1H, CH); 8.00 (d, 1H, CH); 7.70–7.40 (m, 4H, CH); 6.95 (d, 2H, CH); 6.80 (s, 1H, CH); 4.20 (s, 1H, CH); 4.15 (s, 1H, CH); 2.66 (s, 6H, CH₃); 2.45 (s, 3H, CH₃); −0.27 (s, 3H, Si—CH₃); −0.29 (s, 3H, Si—CH₃).

Synthesis of dimethylsilyl{(2-methylcyclopenta[a]naphthalene)-7-(2,5-dimethylcyclopenta[2-b:4,3-b′]-dithiophene) }zirconium dichloride C-40

A solution of (2-methylcyclopenta[a]naphthalen-3-yl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane (4.07 g, 9.2 mmol) in 100 mL of ether was treated at −70° C. with a 1.6 M n-BuLi solution in hexane (15 mL, 24 mmol). The resulting suspension was stirred for additional 2 h at room temperature, then cooled again to −70° C. and added of ZrCl₄ (2.79 g, 12 mmol). The reaction mixture was allowed to warm to room temperature and stirred overnight. The orange precipitate was filtered, washed twice with ether, dried and then recrystallyzed from CH₂Cl₂. Yield 2.77 g (50%).

¹H-NMR (δ, ppm, CD₂Cl₂): 8.00 (d, 1H, CH); 7.70 (d, 1H, CH); 7.60 (d, 1H, CH); 7.55 (t, 1H, CH); 7.48 (t, 1H, CH); 7.25 (s, 1H, CH); 7.15 (d, 1H, CH); 6.78 (q, 1H, CH); 6.65 (q, 1H, CH); 2.60 (d, 3H, CH3); 2.55 (d, 3H, CH₃); 2.40 (d, 3H, CH₃); 1.32 (s, 3H, Si—CH₃); 1.18 (s, 3H, Si—CH₃).

Example 34 Synthesis of dimethylsily {(1-indenyl)-7-(2,5-ditrimethylsilyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride C-13

The C13-ligand synthesis was carried out by coupling the lithium salt of 2,5-ditrimethylsilyl-7H-cyclopenta[1,2-b:4,3-b′]dithiophene with chloro(1-indenyl)dimethyl silane. A suspension of 1.48 g (3 mmol) of (1-indenyl)-7-{(2,5-ditrimethylsilyl-cyclopenta[1,2-b:4,3-b′]dithiophene)}dimethylsilane in 50 mL of ether was treated at −70° C. with 4.1 mL of a 1.6 M n-BuLi solution (6.5 mmol). After the addition, the reaction mixture was allowed to warm to 0° C. and added of 0.75 g (3.2 mmol) of ZrCl₄. The resulting mixture was allowed to reach room temperature and stirred overnight. Then the red precipitate obtained was filtered, washed twice with ether, dried and finally recrystallyzed from CH₂Cl₂. Yield 1.38 g (70%).

¹H-NMR (δ, ppm, CD₂Cl₂): 7.90–6.90 (m, 7H, CH); 6.10 (m, 1H, CH); 1.40 (s, 3H, Si—CH₃); 1.10 (s, 3H, Si—CH₃); 0.41 (s, 9H, Si(CH₃)₃); 0.20 (s, 9H, Si(CH₃)₃).

Example 35 Synthesis of (3-methyl-4-trimethylsilyl-1-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane

A solution of 1.03 g (5.0 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b′]-dithiophene in 40 mL of ether was treated at −70° C. with 3.13 mL of a 1.6 M n-BuLi solution (5.0 mmol). After the addition, the mixture was allowed to warm to room temperature and stirred for additional1 h at this temperature. Then it was cooled again to −70° C. and added of a solution of 1.22 g (5 mmol) of chlorodimethyl(3-methyl-4-trimethylsilyl-1-cyclopentadienyl)silane in 10 mL of ether. The resulting mixture was allowed to reach room temperature and stirred overnight. The ligand (3-methyl-4-trimethylsilyl-1-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)dimethylsilane was not isolated, but used in solution for the catalysts synthesis (see below).

Synthesis of dimethylsilyl{(3-methyl-4trimethylsilyl-1-cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b′]-dithiophene)}zirconium dichloride [C-32]

The ligand solution coming from the previous step was treated at −70° C. with 6.3 mL of a 1.6 M n-BuLi solution (10.1 mmol). After the addition, the reaction mixture was allowed to reach room temperature and stirred for additional 50 min at this temperature. The solvent was removed under reduced pressure and the dilithium salt obtained was suspended in hexane. After cooling to −70° C., 1.17 g (5.0 mmol) of ZrCl₄ were added. The reaction mixture was stirred at room temperature overnight, the yellow precipitate was filtered, washed twice with hexane, dried and finally recrystallized from Et₂O. Yield 0.90 g (31%).

¹H-NMR (δ, ppm, CD₂Cl₂): 6.95 (q, 1H, CH, J=1.17 Hz); 6.91 (q, 1H, CH, J=1.17 Hz); 5.77 (d, 1H, CH, J=2.74 Hz); 5.68 (d, 1H, CH, J=2.74 Hz); 2.62 (q, 3H, CH₃, J=1.17 Hz); 2.59 (q, 3H, CH₃, J=1.17 Hz); 2.22 (s, 3H, CH₃); 0.91 (s, 3H, Si—CH₃); 0.89 (s, 3H, Si—CH₃); 0.22 (s, 9H, Si—(CH₃)₃).

Polymerization Examples General Procedures

The cocatalyst methylalumoxane (MAO) was a commercial product which was used as received (Witco AG, 10% wt/vol toluene solution, 1.7 M in Al). The catalyst mixture was prepared by dissolving the desired amount of the metallocene with the proper amount of the MAO solution, obtaining a solution which was stirred for 10 min at ambient temperature before being injected into the autoclave.

Polymerization Examples 1–33 Propylene Polymerization

1 mmol of Al(i-Bu)₃ (as a 1M solution in hexane) and 290 g of propylene were charged at room temperature in a 1-L jacketed stainless-steel autoclave, equipped with magnetically driven stirrer and a 35-mL stainless-steel vial, connected to a thermostat for temperature control, previously purified by washing with an Al(i-Bu)₃ solution in hexanes and dried at 50° C. in a stream of propene. The autoclave was then thermostatted at 2° C. below the polymerization temperature, and then the toluene solution containing the catalyst/cocatalyst mixture was injected in the autoclave by means of nitrogen pressure through the stainless-steel vial, the temperature rapidly raised to the polymerization temperature and the polymerization carried out at constant temperature for 1 hour. After venting the unreacted monomer and cooling the reactor to room temperature, the polymer was dried under reduced pressure at 60 ° C. The polymerization conditions and the characterization data of the obtained polymers are reported in Table 1.

Polymerization Example 34 Propylene/Butene Copolymerization

Operating as in the case of propylene homopolymerizations, 1 mmol of Al(i-Bu)₃ (as a 1M solution in hexane), 160 g of propylene and 154 g of 1-butene were charged at room temperature in the 1-L jacketed stainless-steel autoclave, thermostatted at 58° C., in order to have a 50/50 mol % in the liquid phase, and then the toluene solution containing the catalyst/cocatalyst mixture (0.5 mg of C-20, 0.45 mmol of MAO, in 3 mL of toluene) was injected in the autoclave by means of nitrogen pressure through the stainless-steel vial, the temperature rapidly raised to the polymerization temperature and the polymerization carried out at constant temperature for 1 hour. 26.5 g of essentially amorphous polymer were recovered, which has I.V.=2.29 dL/g, T_(g)=-13.6° C., and butene=27.7 wt % (22.3 mol %).

Polymerization Example 35 Propylene/Ethylene Copolymerization

Operating as in the case of propylene homopolymerizations, 1 mmol of Al(i-Bu)₃ (as a 1M solution in hexane), propylene and ethylene were charged at room temperature in the 1-L jacketed stainless-steel autoclave, thermostatted at 58° C., in order to have a liquid phase composition of 288 g propylene and 1.5 g ethylene (0.42% wt) in the liquid phase, and then the toluene solution containing the catalyst/cocatalyst mixture (0.3 mg of C-20, 0.27 mmol of MAO, in 3 mL of toluene) was injected in the autoclave by means of nitrogen pressure through the stainless-steel vial, the temperature rapidly raised to the polymerization temperature and the polymerization carried out at constant temperature and pressure (25 bar-g) by feeding ethylene (13.3 g total absorption) for 1 hour. 52.7 g of essentially amorphous polymer were recovered, which has I.V.=1.23 dL/g, and ethylene=6.3 wt % (9.2 mol %).

Polymerization Example 36 Propylene Polymerization with Supported Catalyst

a) Preparation of the Supported Catalyst

The apparatus used for the supportation is a glass cylindrical vessel mechanically stirred in order to allow a good mixing between the carrier and the catalytic solution during the impregnation operation. 6 g of a porous polyethylene having I.V. 21 dL/g, mean Particle size 386 μm and porosity 50.9% VN (1.07 cc/g) was loaded into the vessel and mechanically suspended under nitrogen flow. The catalytic solution was prepared by dissolving 24 mg of C-20 in 12 mL of a MAO solution (WITCO, 100 g/L in toluene). Due to the limited porosity of the carrier the liquid is dropped onto the solid until the incipient wetness condition is reached. At this point the solvent is evaporated off under vacuum. All the operations are carried out at room temperature. The catalytic solution is then added to the carrier step by step. The final catalyst appears as a pink-violet free flowing solid with the following composition: Al 5.0% w and Zr 0.0705% w (Al/Zr molar ratio 240).

b) Polymerization

A 4L stainless-steel reactor, equipped with a blade turbine magnetic stirrer, pressure indicator, temperature indicator and a thermosetting jacket, was used. A batch polymerization was carried with the following procedure. 1200 g of liquid monomer was loaded at 30° C., followed by 3 ml of a TIBA solution 100 g/l in hexane used as a scavenger. The polymerization was started by injecting 305 mg of the catalyst into the autoclave at 30° C., by means of nitrogen overpressure, then the temperature was raised up to 60° C. in 10 minutes and maintained for 1 hour. The polymerization was stopped by venting and cooling the reactor. No significant fouling was observed. The product obtained was collected and dried in an oven flushed with nitrogen at 70° C. for 3 hours. 360 g of polymer was obtained with a good morphology having an I.V. of 1.94 dL/g. The activity of the catalyst was 1.2 kg PP/g cat supp.h, corresponding to 1.7 ton PP/gZr.h.

d) Physical Characterization

The polymer was additivated with the reported stabilisation formula and pelletised with the following processing parameters:

Stabilisation Formula

Components Kg CALCIUM STEARATE M 0.0500 FLI-PP 99.7500 IRGANOX B215/ANOX BB 021 0.1500 VASELIN OIL OB 30 0.0500 single screw extruder: MACGI 14 mm diameter Cylinder Temperature: 230° C. Feeding Temperature: 230° C. Screw speed: 50 rpm The so obtained pellets were compression moulded with Carver press Compression moulding: Plaque thickness:

Haze, Gloss, DMTA: 1.0 mm Tensile test: 2.0 mm Notched Izod: 3.2 mm

-   -   Press Plaque Temperature: 200° C.     -   Preheating time (no press): 5 min     -   Pressure time: 5 min     -   Pressure: 14 bar     -   Cooling: rapid in ice/water bath

The plaques, after compression moulding were stored at room temperature at least 48 hours before characterisation.

DSC measurement: obtained with a Mettler calorimeter with the following procedure:

First run: Heating the sample from −120 to 200° C. at 20° C./min

Crystallisation: Cooling from 200° C. to −120° C. at 20° C./min

Second run: Heating the sample from −120 to 200° C. at 20° C./min

The physical characterization of the polymer is reported at table 2.

Polymerization Examples 37–59 Ethylene/Propylene Polymerization

The Ethylen Propylene mixtures were prepared in a 5 L steel cylinder, filled with quantities of the two gases small enough to prevent their condensation. The composition of the gaseous mixture in the cylinder was controlled through GC analysis. The copolymerizations were carried out at 50° C. in a 250 mL glass reactor equipped with a mechanical stirrer, an Allihn condenser, a thermometer and a pipe for monomers feeding, and kept in a thermostatic bath. First, 100 mL of toluene and 3.5 mmol of TIOAO solution were introduced into the nitrogen-purged reactor. At the polymerization temperature, the nitrogen was removed and replaced with the comonomers mixture, with a flow rate of 1.5 L/min. When the equilibrium pressure (1.1 atm of total pressure) was reached, 3.5 μmol of the metallocene dissolved in 5 mL of hexane in the presence of a 35 μmol of TIOA (35 μL of solution 1 M), was added to start the polymerization. During the reaction, the temperature was kept within 50±1° C. After 15 min the polymerization was quenched by adding 1 mL of methanol, and the copolymer was precipitated with 300 m L of methanol acidified with HCl, filtered, washed and dried overnight in vacuo at 50° C. Polymerization results characterization and reactivity ratios r1 and r2 of ethylene/propylene copolymers are reported in tables 3, 4 and 5.

Polymerization Example 60 Ethylene Polymerization with Supported Catalyst

A 4L stainless-steel reactor, equipped with a blade turbine magnetic stirrer, pressure indicator, temperature indicator, feed line for monomer equipped with a thermal-mass flowmeter for the measure of the ethylene uptake and a thermosetting jacket, was used. A batch polymerization was carried out with the following procedure. 1600 ml of liquid propane is loaded into the reactor at 30° C., followed by 2.5 mmoles of tri-isobutylaluminum as the scavenger. The autoclave was pressurized with an ethylene partial pressure of 5 bar. The polymerization was started by injecting 162 mg of the catalyst prepared in example 37 a) into the autoclave at 30° C., by means of nitrogen overpressure. A prepolymerization step was carried out at 30° C. for 30 minutes. After this time the reactor temperature was increased up to 75° C. and the ethylene partial pressure also was increased to 10 bar. The polymerization was stopped after 2 hours by venting and cooling the reactor. The polymer discharged was dried in an oven flushed with nitrogen at 70° C. for 3 hours. 90 g of polymer was obtained with an intrinsic viscosity of 4.29 dL/g and a melting temperature of 141.40° C.

TABLE 1 propylene polymerization Activity MAO/Zr I.V. AH Ex. Cat. mg Yield kg/(gcat.h) molar THN (dL/g) Tm (° C.) (J/g) mm %  1* C-0 2 147 73 3000 0.65 amorphous — 6.7  2 C-1 0.8 87 153 3000 0.54  80 13 58.7  3 CH-1 2 23 12 1000 0.77 amorphous 20 55.5 (TmI = 63)  4* C-3 1 61 122 3000 0.58 139 91 89.2  5* C-4 1 24 24 1000 0.19 148 98 94.3  6* C-5 0.5 69.2 138 1000 0.57 amorphous — 24.8  7 C-2 0.3 87 290 500 0.82 103 40 73.1  8 C-8 1 31 30 500 0.64 — — 50.6  9 C-16 1 44 44 500 0.74 amorphous — 54 10 C-7 1 81 81 500 0.88 107 47 76 11 C-17 1 120 120 500 1.06  80 19 66.5 12 C-9 1 300 300 500 0.72 amorphous — 30.8 13 C-19 1 160 190 500 0.83 amorphous — — 14 C-11 1 240 240 500 0.9 amorphous — 42.6 15 C-14 1 13 13 500 0.84 amorphous — — 16 C-12 1 94 94 500 0.79 amorphous — — 17 C-18 1 64 64 500 1.24 123 62 84 18 C-15 1 60 119 500 0.8 amorphous — — 19 C-10 1 36 36 500 1.25 114 61 79.9 20 C-36 1 42 41.9 500 1.43  93 28 72 21 C-20 1 79 79 500 2.34 115 50 82.1 22 C-34 1 63 63 500 1.69 120 61 82.3 23 C-35 1 12 12 500 1.42 — — — 24^(§) C-28 2.5 125 50 1000 1.19 146 88 93.7 25^(§) C-31 3.5 150 43 1000 0.55 111 55 77.1 26^(§) C-27 2.4 320 133 1000 1.24 126 73 84.9 27 C-29 0.3 38 138 500 2.38 123 67 — 28^(§) C-30 2.4 490 204 1000 0.86 137 83 90.5 29 C-33 1 87 87 500 1.86 139 86 91.7 30^(#) C-37 2 39 19.5 500 1.29 121 67 84.6 31^(#) C-38 1 74 74 500 1.48 121 70 81.8 32^(#) C-39 1 148 148 500 1.75 137 82 90.4 33^(#) C-40 1 140 140 500 2.09 119 63 82.9 Polymerization was carried out at 60° C. For examples 2 and 6 the polymerization time is 0.75 hour; for examples 14 the time is 0.85 hour; for example 27 the time is 0.92 hour; for all the other examples the polymerization time is 1 hour. *Comparative ^(#)Polymerization was carried out in a 2 L reactor with 620 g of liquid propylene ^(§)Polymerization was carried out in a 4 L reactor with 1200 g of liquid propylene

TABLE 2 polypropylene characterization Description Units Value Melt Flow Rate “L” METHOD ASTM D1238 g/10′ 2.100 HAZE on 1 mm compresion moulded plaque % 26.0 METHOD ASTM D1003 GLOSS (60 °) HAZE on 1 mm Compresion moulded % 81.0 plaque METHOD ASTM 2457 DSC measurement: Melting temperature (second run) ° C. 113.6 Melting enthalpy (second run) J/g 56.7 CRISTALLIZZATION temperature ° C. 71.5 Crystallisation enthalpy J/g 57.5 Dynamical mechanical analysis DMTA - tensile configuration METHOD ASTM D4065 Tensile modulus at 23° C. Mpa 500 temperaturerature gradient   C./min 2.0 Compresion moulded Quenched Thickness plaque 1 mm Glass transition ° C. 10 temperature Tensile test: Elongational properties - METHOD ASTM D638 Elongation at break % 670 Elongation at yield % 21.0 Strength at break Mpa 27.0 Strength at yield Mpa 16.0 Specimen width mm 5.98 SPAN mm 25 TEMPERATURE ° C. 23 Elongation speed mm/min 500.00 RHEOLOGY MEASUREMENTS VIA DYNAMIC VISCOSIMETRY Polydispersity Index — 2.4 Frequency range 0.01–100 rad/s TEMPERATURe ° C. 200.0

TABLE 3 Ethylene/propylene copolymerization with thiocene/TIOAO catalytic systems Ethylene/Propylene^(a) Copolymer gas phase liquid phase Activity I.V. [η] Composition^(b) Ex. Metallocene mol/mol mol/mol Kg_(pol)/g_(cat)h dL/g Ethylene, % wt 37 C-4 2.46 0.582 1.2 2.01 79.25 38 C-4 1.16 0.274 0.4 0.90 66.94 39 C-9 2.60 0.614 3.7 1.09 72.59 40 C-9 1.17 0.277 0.5 n.m^(c) 68.29 41 C-13 2.21 0.522 0.8 1.50 90.33 42 C-13 1.16 0.274 0.2 1.00 82.57 43 C-20 2.60 0.614 3.4 1.50 72.08 44 C-20 1.17 0.277 8.4 0.96 53.96 45 C-27 2.52 0.596 7.7 1.85 63.49 46 C-27 1.19 0.282 7.4 1.41 52.49 47 C-29 2.52 0.596 3.9 2.15 71.00 48 C-29 1.19 0.282 0.4 1.57 64.91 49 C-30 1.82 0.432 3.3 1.35 74.34 50 C-30 1.19 0.282 1.2 1.08 62.25 51 C-32 1.82 0.432 4.5 1.94 84.31 52 C-32 1.19 0.282 0.9 1.42 76.83 53 C-32 1.82 0.432 5.1 1.73 79.37 54 C-32 1.43 0.338 2.4 1.41 76.04 55 C-33 1.82 0.432 2.5 n.m.^(c) 77.51 56 C-33 1.43 0.338 8.9 1.31 n.m.^(c) 57 C-34 1.82 0.432 9.4 0.88 57.00 58 C-34 1.43 0.338 9.6 0.81 47.09 59 C-35 1.82 0.432 0.3 1.31 75.32 ^(a)Molar ratio of the monomers in the gas and in the liquid phases ^(b)from ¹³C NMR analysis. ^(c)not measured.

TABLE 4 ¹³C NMR characterization of ethylene/propylene copolymers. [E] [PPP] [PPE] [EPE] [PEP] [EEP] [EEE] r₁r₂ Ex. Metallocene molar fraction 37 C-4 0.8514 0.0000 0.0386 0.1100 0.0181 0.2066 0.6267 0.92 38 C-4 0.7523 0.0180 0.0844 0.1453 0.0725 0.2814 0.3984 0.91 39 C-9 0.7989 0.0089 0.0524 0.1398 0.0363 0.2621 0.5005 0.75 40 C-9 0.7636 0.0060 0.0694 0.1609 0.0589 0.2946 0.4101 0.62 41 C-13 0.9334 0.0000 0.0190 0.0476 0.0000 0.1080 0.8254 2.85 42 C-13 0.8766 0.0000 0.0502 0.0732 0.0118 0.1790 0.6858 2.45 43 C-20 0.7948 0.0058 0.0682 0.1312 0.0291 0.2642 0.5015 0.96 44 C-20 0.6374 0.0568 0.1628 0.1429 0.0811 0.2889 0.2674 1.07 45 C-27 0.7229 0.0106 0.0974 0.1691 0.0735 0.2941 0.3553 0.66 46 C-27 0.6237 0.0334 0.1588 0.1840 0.1091 0.2933 0.2213 0.59 47 C-29 0.7860 0.0000 0.0620 0.1519 0.0381 0.2800 0.4679 0.63 48 C-29 0.7351 0.0078 0.0843 0.1729 0.0541 0.3009 0.3801 0.58 49 C-30 0.8129 0.0000 0.0598 0.1272 0.0357 0.2620 0.5152 0.91 50 C-30 0.8326 0.0000 0.0193 0.1481 0.0239 0.2482 0.5605 0.27 51 C-32 0.8896 0.0000 0.0048 0.1056 0.0197 0.1976 0.6723 0.16 52 C-32 0.7121 0.0147 0.1133 0.1598 0.0624 0.3127 0.3370 0.79

TABLE 5 Reactivity ratios r₁ and r₂, and their product r₁r₂ for ethylene/propylene copolymerization Example Metallocene r₁ r₂ r₁r₂ 37 C-4 10.1 ± 0.3  0.08 ± 0.01 0.8 ± 0.1 39 C-9 7.8 ± 1.2 0.06 ± 0.04 0.5 ± 0.4 41 C-13 28.9 ± 0.7  0.09 ± 0.01 2.6 ± 0.4 43 C-20 6.0 ± 0.2 0.16 ± 0.02 1.0 ± 0.1 45 C-27  43 ± 0.4 0.13 ± 0.03 0.6 ± 0.2 47 C-29 7.0 ± 1.0 0.07 ± 0.04 0.5 ± 0.3 

1. A metallocene compound of general formula (I): LGZMXp  (I) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, which can form a ring having 3 to 8 atoms optionally bearing a substituent; Z is a moiety of formula (II):

wherein R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in an allowed position; G is a moiety of formula (III):

wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are selected from hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen; M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements, X, which may be the same or different, is a hydrogen atom, halogen atom, a group R¹⁰, OR¹⁰, OSO₂CF₃, OCOR¹⁰, SR¹⁰, NR¹⁰ ₂ or PR¹⁰ ₂, wherein the substituents R¹⁰ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms; p is an integer of from 1 to 3, being equal to the oxidation state of the metal M minus 2; with the proviso that said metallocene compound is different from: isopropylidene (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3 ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-n-butylcyclopentadienyl)(7-cyclopenaditiophene)zirconium dichloride, isopropylidene (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride and dimethylsilanediyl (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride.
 2. The metallocene according to claim 1, wherein the transition metal M is selected from titanium, zirconium or hafnium.
 3. The metallocene according to claim 1, wherein L is CMe₂ or SiMe₂.
 4. The metallocene according to claim 1, wherein A or B is a sulfur atom and the other is a CH group.
 5. The metallocene according to claim 1, wherein R³ and R⁴ are the same and are a C₁–C₂₀-alkyl group, which can contain a silicon atom.
 6. The metallocene according to claim 1, wherein G is a moiety of formula (IIIa):

wherein R⁶ and R⁹ equal to or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements; R⁷ is a C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl or a QR¹¹R¹²R¹³ group, wherein Q is C, Si, or Ge; R¹¹, R¹² and R¹³, which may be the same as or different from each other, are hydrogen, C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radicals, optionally containing a heteroatom, with the proviso that when Q is a carbon atom, at least one of R¹¹, R¹² and R¹³ is a hydrogen atom.
 7. The metallocene according to claim 6, wherein R⁷ is a phenyl, a CHR¹¹R¹² or a SiR¹¹R¹²R¹³ group, wherein R¹¹, R¹² and R¹³ are hydrogen or C₁–C₂₀-alkyl groups.
 8. The metallocene according to claim 1, wherein G is a moiety of formula (IV):

wherein T¹ is a sulfur atom or a CR¹⁶ group; T² is a carbon atom or a nitrogen atom; z is 1 or 0; the ring containing T¹ and T² has double bonds in the allowed position; with the proviso that if z is 1, T¹ is a CR¹⁶ group and T² is a carbon atom and the ring formed is a benzene ring; and if z is 0, T² bonds directly the cyclopentadienyl ring, the 5 membered ring formed has double bond in any of the allowed positions having an aromatic character and T¹ and T² are not at the same time, a sulfur atom and a nitrogen atom, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, same or different, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms optionally bearing substituents.
 9. The metallocene according to claim 8, wherein G is a moiety of formula (IVa):

wherein R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms, and any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, can form a ring comprising 4 to 8 atoms optionally bearing substituents and the benzene ring optionally being perhydrated.
 10. The metallocene according to claim 9, wherein G is a moiety of formula (IVb)

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and any of two adjacent R¹⁵, R¹⁶, R¹⁷, R¹⁸ can form a ring comprising 4 to 8 atoms optionally bearing substituents; R¹⁴ being a C₁–C₂₀-alkyl or C₆–C₂₀-aryl group.
 11. The metallocene according to claim 9, wherein G is a moiety of formula (IVc)

wherein R¹⁴, R¹⁶, R^(17,) and R¹⁸ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and optionally any of two adjacent R¹⁶, R¹⁷, and R¹⁸ can form a ring comprising 4 to 8 atoms optionally bearing substituents; R¹⁹ is a C₁–C₂₀-alkyl or C₆–C₂₀-aryl group or forms with R¹⁸ a benzene ring optionally bearing substituents.
 12. The metallocene according to claim 11, wherein R¹⁴ is a C₁–C₂₀-alkyl or C₆–C₂₀-aryl group.
 13. The metallocene according to claim 11, wherein R¹⁶ is a C₁–C₂₀-alkyl or C₆–C₂₀-aryl.
 14. The metallocene according to claim 8, wherein G is a moiety of formula (IVd):

wherein T¹ is a sulfur atom or a CR¹⁶ group; T² a carbon atom or a nitrogen atom; the 5 member ring formed by T¹ and T² has double bonds in any of the allowed positions, having an aromatic character; with the proviso that if T¹ is a sulphur atom T² is not a nitrogen atom; R¹⁴, R¹⁷ and R¹⁸ which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements and R¹⁷and R¹⁸ can form a ring comprising 4 to 8 atoms optionally bearing substituents.
 15. The metallocene according to claim 14 wherein T² is a carbon atom; T¹ is a sulphur atom and R¹⁴, R¹⁷ and R¹⁸ equal to or different from each other are a C₁–C₂₀-alkyl, or C₆–C₂₀-aryl.
 16. A ligand of formula (V): LG′Z′  (V) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z′ is a moiety of formula (VI):

or its double bond isomers; wherein the double bonds are in an allowed position; R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in the allowed position; G′ is a moiety of formula (VII):

or its double bond isomers; wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen.
 17. A process for the preparation of a ligand of formula (V): LG′Z′  (V) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z′ is a moiety of formula (VI):

or its double bond isomers; wherein the double bonds are in an allowed position; R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in the allowed position; G′ is a moiety of formula (VII):

or its double bond isomers; wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen; comprising the following steps: a) contacting a compound of the formula (VIII) with a base selected from the group consisting of metallic sodium and potassium, sodium and potassium hydroxide and an organic lithium compound, wherein the molar ratio between the compound of the formula (VIII) and said base is at least 1:1;

 wherein R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ the rings containing A and B have a double bond in the allowed position; b) contacting the obtained anionic compounds of the formula from step a) with a compound of formula (IX):

 wherein  R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen; and then (c) treating the obtained product from step b) with a protonating agent.
 18. A process for the preparation of a ligand of formula (V): LG′Z′  (V) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z′ is a moiety of formula (VI):

or its double bond isomers; wherein the double bonds are in an allowed position; R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in the allowed position; G′ is a moiety of formula (VII):

or its double bond isomers; wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen; comprising the following steps: a) contacting a compound of the formula (VIII) with a base selected from the group consisting of metallic sodium and potassium, sodium and potassium hydroxide and an organic lithium compound, wherein the molar ratio between the compound of the formula (VIII) and said base is at least 1:1

 wherein R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in the allowed position; b) contacting the obtained anionic compounds from step a) with a compound of formula (IX):

wherein Y is a halogen radical selected from the group consisting of chloride, bromide and iodide; L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ not hydrogen.
 19. A process for the preparation of a metallocene compound of general formula (I): LGZMXp  (I) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z is a moiety of formula (II):

wherein R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in an allowed position; G is a moiety of formula (III):

wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen; M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements, X, which may be the same or different, is a hydrogen atom, halogen atom, a group R¹⁰, OR¹⁰, OSO₂CF₃, OCOR¹⁰, SR¹⁰, NR¹⁰ ₂ or PR¹⁰ ₂, wherein the substituents R¹⁰ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms; p is an integer of from 1 to 3, being equal to the oxidation state of the metal M minus 2; with the proviso that said metallocene compound is different from: isopropylidene (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride and dimethylsilanediyl (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride; said process comprising contacting the ligand of general formula (V) LG′Z′  (V) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z′ is a moiety of formula (VI):

or its double bond isomers; wherein the double bonds are in any of the allowed positions; R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in the allowed position; G′ is a moiety of formula (VII):

or its double bond isomers; wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ being capable of forming a ring comprising from 3 to 8 atoms, optionally having substituents, with the proviso that R⁷ is different from R⁸ and when R⁷ is a tert-butyl radical, R⁸ is not hydrogen; with a base capable of forming a corresponding dianionic compound and thereafter with a compound of general formula MX_(p+2), wherein M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements, X, which may be the same or different, is a hydrogen atom, halogen atom, a group R¹⁰, OR¹⁰, OSO₂CF₃, OCOR¹⁰, SR¹⁰, NR¹⁰ ₂ or PR¹⁰ ₂, wherein the substituents R¹⁰ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms; and p is an integer of from 1 to 3, being equal to the oxidation state of the metal M minus
 2. 20. A catalyst obtained by contacting: (A) a metallocene compound of formula (I) LGZMX_(p)  (I) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z is a moiety of formula (II):

wherein R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in an allowed position; M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements, X, which may be the same or different, is a hydrogen atom, halogen atom, a group R¹⁰, OR¹⁰, OSO₂CF₃, OCOR¹⁰, SR¹⁰, NR¹⁰ ₂ or PR¹⁰ ₂, wherein the substituents R¹⁰ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms; p is an integer of from 1 to 3, being equal to the oxidation state of the metal M minus 2; with the proviso that said metallocene compound is different from: isopropylidene (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride and dimethylsilanediyl (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride; and G is a moiety of formula (III):

wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents; with the proviso that R⁷ is different from R⁸ and when R⁷ is a tertbutyl radical R⁸ is not hydrogen; and (B) at least one of an alumoxane and a compound capable of forming an alkyl metallocene.
 21. The catalyst according to claim 20 wherein in the metallocene compound of formula (I) G is a moiety of formula (IIIa)

wherein R⁶ and R⁹ equal to or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements R⁷ is a C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl or a QR¹¹R¹²R¹³ group, wherein Q is C, Si, or Ge; R¹¹, R¹² and R¹³, which may be the same as or different from each other, are hydrogen, C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radicals, optionally containing a heteroatom, with the proviso that when Q is a carbon atom, at least one of R¹¹, R¹² and R¹³ is a hydrogen atom, or formula (IV)

wherein T¹ is a sulfur atom or a CR¹⁶group; T² is a carbon atom or a nitrogen atom; z is 1 or 0; the ring containing T¹ and T² has double bonds in the allowed position; with the proviso that if z is 1, T¹ is a CR¹⁶ group and T² is a carbon atom and the ring formed is a benzene ring; and if z is 0, T² bonds directly the cyclopentadienyl ring, the 5 membered ring formed has double bond in any of the allowed positions having an aromatic character and T¹ and T² are not at the same time, a sulfur atom and a nitrogen atom, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, same or different, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms optionally bearing substituents.
 22. The catalyst according to claim 21 wherein in the metallocene compound of formula (I) G is a moiety selected from the compound of formula (IVa),

wherein R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, which maybe the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms, and any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms optionally bearing substituents and the benzene ring optionally being perhydrated, formula (IVb),

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and any of two adjacent R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ can form a ring comprising 4 to 8 atoms optionally bearing substituents; R¹⁴ being a C₁–C₂₀-alkyl or C₆–C₂₀-aryl group, formula (IVc),

wherein R¹⁴, R¹⁶, R¹⁷, and R¹⁸ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, and optionally any of two adjacent R¹⁴, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ can form a ring comprising 4 to 8 atoms optionally bearing substituents; R¹⁹ is a C₁–C₂₀-alkyl or C₆–C₂₀-aryl group or forms with R¹⁸ a benzene ring optionally having substituents, or formula (IVd)

wherein T¹ is a sulfur atom or a CR¹⁶ group; T² is a carbon atom or a nitrogen atom; the 5 member ring formed by T¹ and T² has double bonds in any of the allowed positions, having an aromatic character; with the proviso that if T¹ is a sulphur atom T² is not a nitrogen atom; R¹⁴, R¹⁷ and R¹⁸ which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements and R¹⁷ and R¹⁸ can form a ring comprising 4 to 8 atoms optionally bearing substituents.
 23. The catalyst according to claim 20, wherein said alumoxane is selected from methylalumoxane (MAO), isobutylalumoxane (TIBAO) or 2,4,4-trimethyl-pentylalumoxane (TIOAO).
 24. The catalyst according to claim 20, wherein the compound capable of forming a metallocene alkyl cation is a compound of formula D⁺E⁻, wherein D⁺ is a Brønsted acid, able to donate a proton and to react irreversibly with a substituent X of the metallocene of formula (I) and E⁻ is a compatible anion, which is able to stabilize the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be able to be removed by an olefinic monomer.
 25. A process for the preparation of a polymer of alpha-olefins comprising contacting one or more alpha-olefins under polymerization conditions with a catalyst obtained by contacting: (A) a metallocene compound of formula (I) LGZMX_(p)  (I) wherein L is a divalent group bridging the moieties G and Z, selected from CR¹R², SiR¹R² or (CR¹R²)₂, wherein R¹ and R², which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom, and can form a ring having 3 to 8 atoms optionally bearing a substituent; Z is a moiety of formula (II):

wherein R³ and R⁴, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom; A and B are sulfur (S), oxygen (O) or CR⁵, wherein R⁵ is hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing a heteroatom with the proviso that if A is S or O, then B is CR⁵ or if B is S or O, then A is CR⁵, and wherein either A or B is different than CR⁵ and the rings containing A and B have a double bond in an allowed position; M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements, X, which may be the same or different, is a hydrogen atom, halogen atom, a group R¹⁰, OR¹⁰, OSO₂CF₃, OCOR¹⁰, SR¹⁰, NR¹⁰ ₂ or PR¹⁰ ₂, wherein the substituents R¹⁰ are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms; p is an integer of from 1 to 3, being equal to the oxidation state of the metal M minus 2; with the proviso that said metallocene compound is different from: isopropylidene (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-trimethylsilylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-n-butylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride, isopropylidene (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride and dimethylsilanediyl (3-i-propylcyclopentadienyl)(7-cyclopentaditiophene)zirconium dichloride; and G is a moiety of formula (III):

wherein R⁶, R⁷, R⁸ and R⁹, which may be the same as or different from each other, are hydrogen, a C₁–C₂₀-alkyl, C₃–C₂₀-cycloalkyl, C₂–C₂₀-alkenyl, C₆–C₂₀-aryl, C₇–C₂₀-alkylaryl, or C₇–C₂₀-arylalkyl radical, optionally containing heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements, at least one of substituent pairs R⁶ and R⁷, and R⁸ and R⁹ can form a ring comprising from 3 to 8 atoms, optionally bearing substituents; with the proviso that R⁷ is different from R⁸ and when R⁷ is a tertbutyl radical R⁸ is not hydrogen; and (B) at least one of an alumoxane and a compound capable of forming an alkyl metallocene.
 26. The process according to claim 25 for the preparation of homo- and copolymers of propylene.
 27. The process according to claim 26 wherein the process is carried out in the presence of an alpha-olefins selected from 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or 1-dodecene.
 28. The process according to claim 25 for the preparation of homo- and copolymers of ethylene.
 29. The process according to claim 28, wherein the process is carried out in the presence of an olefin selected from propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, allylcyclohexane, cyclopentene, cyclohexene and norbornene, 1,5-hexadiene, 1-6-heptadiene, 2-methyl-1,5-hexadiene, trans 1,4-hexadiene, cis 1,4-hexadiene, 6-methyl-1,5-heptadiene, 3,7-dimethyl-1,6-octadiene, 11-methyl-1,10-dodecadiene, or 5-ethylidene-2-norbornene.
 30. The process according to claim 25 wherein the catalyst is supported on an inert carrier.
 31. The process according to claim 25 characterized in that it is carried out in gas phase.
 32. A propylene homopolymer having the following characteristics: triads (mm) satisfy the relation 55<mm<85; melting enthalpy (ΔH) of between 5 J/g and 70 J/g. Haze (ASTM 2457) from 15% to 30%; Gloss (60° C.) (ASTM 2457) from 60% to 95%; Tensile modulus (ASTM D4065) from 1000 MPa to 200 MPa; Elongation at break (ASTM D4065) from 300% to 900%; Strength at break (ASTM D638) from 10% to 40% wherein the propylene homopolymer is produced using the catalyst of claim
 20. 33. A propylene copolymer containing from 0.1 to 30% by moles of units deriving from an olefin of formula CH₂═CHR′, R′ being hydrogen, a C₂–C₂₀-alkyl or a C₆–C₁₂-aryl group, said propylene copolymer having the following characteristics: melting enthalpy <70 J/g; triads (mm) satisfy the relation: 30<mm<85 wherein the propylene copolymer is produced using the catalyst of claim
 20. 34. The propylene copolymer according to claim 33 wherein the olefin of formula CH₂═CHR′ is ethylene.
 35. The metallocene compound according to claim 1 wherein at least one of R³ and R⁴ is different than hydrogen. 